Evidence for cathodic electrodeposition of radon species

Phase change effects on the total organic yield have been studied in crystalline chlorobenzene derivatives activated by radiative neutron capture. Irradiation of the compounds in benzene solution decreased the organic yield considerably while these values remained unchanged when 11 benzene + DMSO or 11 benzene + acetonitrile solvent mixtures were used, the 11 benzene + THF solvent gave the lowest yield in all the cases. Heat treatment to the neutron activated solids enhanced the organic yield only in the case of 2-amino 5-chlorobenzophenone by 7%.     

Electrical conductivity and phase transition studies of some selected Congo red-metal complexes

The electrical properties of Congo Red dye (L) and its metal (M) complexes ofML molar ratios of 11 and 21, whereM=Cr(III), Fe(lII), Cu(II), Zn(II), Zr(IV), Th(IV) and UO₂(II), indicated semiconducting behaviour. The activation energies and electrical conductivities depend on the ionic charge of the metal chelates. The activation energies of 11 metal complexes are greater than those of 21 metal complexes. The conductivity data obtained are interpreted on the basis of the molecular structure of the Congo Red complexes. One phase transition was obtained during DTA study of Congo Red dye at 212°C. This phase transition may be due to the rotation of the two naphthalene rings and the N=N groups around the diphenyl group centre.     

Effect of alkali ions (Na+, K+) on the solvent extraction of uranium(VI) with a di-carboxylated calix[4] arene

The solvent extraction of uranium(VI) with a di-carboxylated calix[4]arne (LH₂) in chloroform and 1,2-dichloroethane has been studied in the presence or absence of alkali ions (M=Na⁺,K⁺). For UO ₂ ²⁺ when studied alone, a 12 (metal: ligand) extracted species is evidenced, with a rather low associated extraction equilibrium constant. The efficiency of extraction increases drastically in the presence of alkali ions, due to the formation of heteronuclear complexes. In all cases, the extracted species are found to be both 122 and 112 (UO ₂ ²⁺ MLH₂) mixed complexes, except in chloroform with K⁺, where only the latter is formed. In the case of Na⁺, mass spectrometry spectra confirm the existence of both homo and heteronuclear complexes as determined in the extraction studies.     

Host-guest interactions in aqueous media withp-tert.-butylcalix[4]arene bearing polyoxyethylene chains

The interactions ofp-tert.-butylcalix[4]arene bearing polyoxyethylene chains (C3) with pyrene (Py), 1-anilino-8-naphthalenesulfonate (ANS) andN-phenyl-naphthylamine (NPN) in aqueous solution were studied by absorption and fluorescence measurements. Absorption spectral changes and fluorescence enhancements reveal that C3, which has a hydrophobic cavity, can include organic molecules and ions in aqueous solution and form 11 host-guest complexes with ANS and NPN. C3 forms inclusion complexes with Py at different stoichiometries depending on the host: guest molar ratio. Binding constants of 2.2×10⁴, 2.0×10⁴ and 3.6×10⁵ dm³ mol^–1 were calculated for the C3Py, C3ANS and C3NPN complexes (11), respectively, based on the Benesi-Hildebrand equation.Author for correspondence.     

Die Reaktion von Ce(III), Th(IV) und U(VI) mit Chinizaringrün und seinem nichtsulfonierten Grundkörper

The reaction of 1,4-(2-sulpho-4-methylanilino)anthraquinone (quinizarin green,QG) and its non-sulphonated derivative (NSQG) with Ce(III), Th(IV), and U(VI) was investigated. Spectrophotometric and conductometric studies were carried out to investigate the stoichiometry of the complexes formed. The studies revealed the formation of 11 and 12 (ML) complexes. The apparent stability constants of the different complexes were determined. The structure of the ligand in the solid chelates was studied by IR spectrophotometry which showed that the chelate formation takes place through the oxygen of the C=O group and the -imino nitrogen.

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Einige analytische Eigenschaften von 1,3-Dimethyl-4,5-diaminouracil

Zusammenfassung 1,3-Dimethyl-4,5-diaminouracil (DAL) hat sich als sehr empfindliches Reagens zum selektiven Nachweis von Co²⁺-Ionen im stark alkalischen Medium einer Phosphatpufferlösung (p_H=11,20) erwiesen. Es wurden vier Additionsverbindungen von DAL mit den Zentralatomen Cd(II), Pd(II), Ni(II) und Co(II) im Verhältnis Me DAL=1 2 hergestellt. Spektrophotometrische Untersuchungen weisen darauf hin, daß bei p_H 6 bis 7 eine Komplexverbindung im Verhältnis CoDAL=12 gebildet wird.

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Summary 1,3-dimethyl-4,5-diaminouracil (DAL) has been found to be a very sensitive reagent for the selective detection of Co²⁺ ions in strong alkaline medium of a phosphate buffer solution (p_H=11.20). Four addition compounds of DAL with the central atoms Cd(II), Pd(II), Ni(II) and Co(II) with the ratio MeDal=12 have been prepared. Spectrophotometric studies indicate that at p_H=6–7, complex compound is produced with the ratio CoDAL=12.

     

Molybdän(VI) -Hydroxylamin- Komplexe. IV

Zusammenfassung 4-(2-Pyridylazo)-resorcin (PAR) bildet mit sechswertigem Molybdän und Hydroxylamin einen ternären, rot gefärbten Komplex. Dieser enthält die Komponenten in einem molaren Verhältnis 111. Die Bildung dieses Komplexes ist die Grundlage für eine sehr empfindliche spektralphotometrische Molybdänbestimmung. Die Kennziffern für diese Reaktion werden angegeben. Störende Fremdmetalle können durch DCTA und Weinsäure maskiert oder durch Extraktion ihrer PAN-Komplexe mit Chloroform abgetrennt werden. Wolfram bildet keinen gefärbten Komplex mit PAR.

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Molybdenum-hydroxylamine complexes. IV

Summary A ternary red complex results from the action of 4-(2-pyridylazo)-resorcinol (PAR) with hexavalent molybdenum and hydroxylamine. This product contains the components in a molar ratio 111. The formation of this complex is the basis for a very sensitive spectrophotometric determination of molybdenum. The characteristics of this reaction are stated. Interfering foreign ions can be masked by DCTA and tartaric acid or removed by extraction of its PAN-complex with chloroform. Tungsten does not yield a colored complex with PAR.

     

Reactivity of oxalates of La(III), Ba(II) and Cu(II) in ternary mixtures

Composites of cuprates of La(III) and Ba(II) were obtained by decomposing mixtures of oxalates of La(III), Ba(II) and Cu(II) prepared in 111 and 123 mol proportions respectively and sintering the oxide products at 1173 K. Reactions studied by TG, DTA and XRD techniques revealed the following features: (i) Decomposition of oxalates of La(III) and Ba(II) is drastically affected in mixtures. Decomposition temperature of organic part in the former (111) is shifted by 100 K while that of BaCO₃ in the case of latter (123) is shifted by 400 K towards lower temperature side. (ii) All exothermic peaks on DTA traces of both the mixtures are allotted to the decomposition of oxalates to Cu₂O, La₂O₂CO₃ and BaCO₃ phases while endothermic peaks around 863 and 1083 K are assigned for BaCuO₂ and La₂CuO₄ phases respectively in the case of former (111) and endothermic peaks at about 1068, 1136 and 1213 K are correlated with BaCuO₂, a composite of La₂O₃, La₂CuO₄ and La_0.5Ba_0.5CuO_3– (0.5) phases and LaBa₂Cu₃O_7– (0) phase respectively in the case of latter (123) and (iii) Lines of all cuprate compounds appear in XRD patterns of those samples preheated at temperatures 873 K. The following reaction is proposed in the case of 123 mixture: Authors are deeply thankful to the Authorities of Department of Atomic Energy (DAE), Goverment of India, for providing the funds for research project and to Professor A. V. Phadke, Department of Geology, University of Poona, for the valuable discussion.     

Über Metallkomplexe heterocyclisch substituierter Formazane und Azomethine

Zusammenfassung Es wurden zwei neue Formazane, und zwar 1-Phenyl-5-(2-carboxyphenyl)-3-(3-methyl-2-chinoxalyl)-formazan und 1-Phenyl-5-(2-carboxyphenyl)-3-(3-methyl-2-chinolyl)-formazan synthetisiert. Diese Verbindungen bilden mit Uranyl-, Kobalt-und Nickelionen gut definierte Komplexe. Bei ihren Uran- und Kobaltkomplexen wurde ein Metall/Formazan-Verhältnis von 12, bei den Nickelkomplexen dagegen 11 festgestellt. Außerdem wurden Kobalt- und Nickelkomplexe des 3-Methylchinoxalin-2-aldehyd-o-hydroxy-anils mit einem Metall/Formazan-Verhältnis von 12 dargestellt.

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Metal complexes of heterocyclic substituted formazans and azomethines

Two new formazans, 1-phenyl-5-(2-carboxyphenyl)-3-(3-methyl-2-quinoxalyl)-formazan and 1-phenyl-5-(2-carboxyphenyl)-3-(3-methyl-2-quinolyl)-formazan have been synthesized. These compounds form well defined complexes with uranyl, cobalt and nickel ions. The ratio of metal/formazan in uranium and cobalt complexes is 12, in nickel complexes 11. Besides, cobalt and nickel complexes of 3-methyl-quinoxaline-aldehyde-o-hydroxy-anil were synthesized with a metal/azomethine ratio of 12.

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Teil der DissertationB. Ocakcioglu, Univ. Istanbul 1969.     

Komplexe des Nickels mit p-Methylbenzamidoxim

Zusammenfassung Die Komplexbildung des p-Methylbenzamidoxims (pMB) mit Ni²⁺ wurde in neutraler und alkalischer Lösung spektrophotometrisch untersucht. In neutraler Lösung wird ein grüner Komplex 11 gebildet, dessen Bildungskonstante ₁=1,12 ist. In alkalischer Lösung werden zwei Komplexe (11 und 12) gebildet mit Bildungskonstanten ₁=4·10⁵ und ₂=0,2.

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Nickel complexes with p-methyl benzamide oxime

The complex formation of p-methyl benzamidoxime with Ni²⁺ was studied spectrophotometrically in neutral and in alkaline solution. A green complex 11 is formed in neutral solution. Its formation constant is ₁=1.12. In alkaline solution two complexes (11 and 12) are formed. Their formation constants are ₁=4·10⁵ and ₂=0,2 resp.

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Thermal analysis of bitumens from black coal,extracted successively with different solvents

A successive extraction of bitumes from black coal was carried out using the following solvents: petroleum ether, petroleumether-benzene (11), benzene, benzene-ethyl ether (11), ethyl ether, ethyl ether ethanole (11), ethanol. These extract organic products as follows: 0.06, 0.16, 0.11, 0.21, 0.07, 0.29 and 0.70% respectively. The obtained by the above mentioned solvents chujniuds were compounds to the thermal and IR-spectral analysis.

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Zusammenfassung Mittels folgender Lösungsmittel wurde eine sukzessive Extraktion von Bitumen aus Steinkohle durchgeführt: Petrolether, Petrolether-Benzol (11), Benzol, Benzol-Ethylether (11), Ethylether, Ethylether-Ethanol (11), Ethanol. In dieser Reihenfolge konnten organische Produkte zu 0.06, 0.16, 0.11, 0.21, 0.07, 0.29 bzw. 0.70 % extrahiert werden. Die durch aufgeführte Lösungsmittel erhaltenen Verbindungen wurden einer Thermound einer IR-Analyse unterzogen.

     

Stabilities and thermodynamics of uranyl(II) and thorium(IV) complexes of 2-mercaptoethanol

The complexation of UO₂ ⁺² and Th⁺⁴ ions with 2-mercaptoethanol has been studied by potentiometric and conductometric titration techniques. Uranyl ion forms 11 and 12 complexes in the pH-range 3.3–6.5 and thorium ion forms 12, 13, and 14 complexes in the pH-range 3.2–4.8 with considerable overlapping. Their logk _stab. values are determined at 10, 20, and 30°C at ionic strength =0.1M (NaClO₄) by applyingCalvin-Melchior's extension of theBjerrum method. The overall changes in thermodynamic functions G, H, and S accompanying complexation determined at 20°C are –19.48 kcal/mole, –22.77 kcal/mole, –11.23 cal/deg·mole for uranyl complexes and –33.94 kcal/mole, –4.93 kcal/mole, 99.00 kcal/deg·mole for thorium complexes, resp.     

Complexes of divalent ions in mixed solvent media. III. Outer-sphere interactions in amine + diluent solutions

The standard enthalpies and (in part) free energies and entropies of transfer from amine (L) to amine + diluent (D) mixtures have been determined for MX₂L₂ complexes at 25°C using chloroform, 1,1,2,2,-tetrachloroethane (TCE), benzene, chlorobenzene, and ethyl acetate as diluents (M=Co and Zn; X=Cl and Br; L = pyridine, -picoline, and -picoline). Thermodynamic functions of transfer indicate specific outer-sphere interactions of the complexes with amine and protic diluents (chloroform and TCE) and reveal solvent-solvent interactions of amine + protic diluent mixtures. The effects of the nature of X, L, and M of the MX₂L₂ complexes on their interaction with the components of the mixed solvent are discussed.Deceased.     

Determination of ten anti-inflammatory drugs in serum by isocratic liquid chromatography

Summary A high performance liquid chromatographic system has been developed for the resolution of ten anti-inflammatory drugs. Isocratic separation was achieved using a Spherisorb 5m ODS column with an eluent consisting of water-orthophosphoric acid to pH 3.2: acetonitrile: methanol (523513). A comparison was made between chloroform/acetonitrile (32) and hexane/ether (11) as solvents for the extraction of these drugs from serum.     

Phosphorus-containing podands. 6. Calorimetric study of complexation of 1,17-bis (diphenylphosphinyl)-3,6,9,12,15-pentaoxaheptadecane with alkali and alkaline-earth metal salts in acetonitrile

1, 17-bis-(Diphenylphosphinyl-3, 6, 9, 12, 15-pentaoxaheptadecane in MeCN forms complexes of 11 and 12 composition (ML) with alkali and alkaline-earth metal salts, complexes of 11 and 21 composition were found for Li salts. The BaL²⁺ complex is the most stable complex, and the complexes NH₄L⁺ and CaL2+ are the least stable. The selectivity for Li is significantly higher for the podand studied than for crown ethers.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 575–581, March, 1991.     

Die extraktiv-photometrische Bestimmung von Palladium als Tetra?thylenglykoldimethyl?ther-tetrajodopalladat(II)

Zusammenfassung Die Flüssig-flüssig-Extraktion des Palladiums als Tetraäthylenglykol-dimethyläther-tetrajodopalladat(II) erlaubt die extraktiv-photometrische Bestimmung von 1,5 g Pd/150 ml Probelösung neben großen Überschüssen an Rhodium (PdRh=150), Ni²⁺, Co²⁺, Mn²⁺ und Zn²⁺ (110⁴). Die Verteilungsbedingungen der Extraktion wurden auf polarographischem Wege untersucht und bewirken eine 100fache Empfindlichkeitssteigerung gegenüber der Kathodenstrahlpolarographie.Der Deutschen Forschungsgemeinschaft danken wir für die apparative und finanzielle Unterstützung der vorliegenden Arbeit.