Ionic Mobility, Structure, Phase Transition, and Conductivity in (NH4)3Sb4F15

Fluoride and ammonium ion dynamics in (NH₄)₃Sb₄F₁₅ was studied by ¹H and ¹⁹F NMR spectroscopy in the range 180-440 K. Types of ionic motion were determined, and their activation energies were estimated. The crystal structure of a single crystal of (NH₄)₃Sb₄F₁₅ (space group ) was solved. In the range K, a reversible phase transition has been found. Based on the experimental values of conductivity of (NH₄)₃Sb₄F₁₅ ( S/cm at T = 440 K), this antimony(III) fluoride is classified as a superionic conductor.     

Solubility of Siderite (FeCO3) in NaCl Solutions

The solubility of siderite (FeCO₃) at 25°C under constant CO₂ partial pressure [p(CO₂)] was determined in NaCl solutions as a function of ionic strength. The dissolution of FeCO₃(s) for the reaction

Absorption spectra and bond type in Co(II) aquoamino complexes

Absorption spectra are reported for solutions containing Co(II) and ammonia. Spectra are calculated for five Co(II) aquoamino complexes. The spectra are used to determine Dq and B, parameters of the bonds in these compounds. It is found that Dq and B change nonlinearly and nonadditively. The parameters _c, Dt, Ds, and have also been established for [Co(H₂O)₆]²⁺ and [Co(NH₃)₆]²⁺. The parameter variation can be explained if the H₂O molecules form weaker bonds to the central atom than do the NH₃ molecules, but are capable of d-p interaction.     

Synthesis and Crystal Structure Investigation of Trinitrotriamminerhodium(III) [Rh(NO2)3(NH3)3]

Synthesis of the complex [Rh(NO₂)₃(NH₃)₃] is described. The compound crystallizes as monoclinic colorless plates. Crystal data: a = 7.176(10), b = 10.407(2), c = 10.989(2) , = 93.27°, V = 819.3(2) ³, space group , Z = 4, d _calc = 2.367 g/cm³. The structure is molecular and built of neutral complexes having cis-facial configuration. The unit cell of the crystal contains two independent complexes.     

Mass transfer in shell-core inorganic TIP1 ion exchanger

The ion exchange processes of (OAc^–) and (OAc^–) proceeding in shell-core inorganic ion exchanger Ti (HPO₄)₂·1/2H₂O has been studied and the diffusion equation whose boundary conditions are satisfied by a shell-core model was solved. Based on the equation solved and experimental data, the diffusion coefficients corresponding to the exchange process (OAc^–) and Li⁺–H⁺ (OAc^–) at 17°C are found to be 7.7×10^–9 and 6.2×10^–8 cm² s^–1 and the activation energies 3.4×10⁴ and 5.0×10³ J mol^–1, respectively. Compared to the gel type of styrene-divinylbenzene strong acid exchanger with 20% cross linking, it can be concluded that the rate of or exchange is 3.5 times faster than that in the organic exchanger.TIP was obtained from the Salt Lake Institute of the Academy of Science of China.     

Insertions of phenylacetylene with chelated bis(triphenylphosphine) - ruthenium(II)hydridocarbonyl complexes

Summary Phenylacetylene reacts stoichiometrically or in excess with the Ru—H bond of RuH(CO)(PPh₃)₂(L) (LH = 2-hydroxypyridine, 2-hydroxy-6-methylpyridine, acetylacetone, benzoylacetone, 2-hydroxyacetophenone, 2-hydroxypropiophenone, 2-hydroxybenzophenone and 4-methoxy-2-hydroxybenzophenone) in boiling benzene to give -vinylic or -vinylalkynyl complexes of the type Ru(CO)-(PPh₃)₂(L)(CH CHPh) and Ru(CO)(PPh₃)₂(L){C-(C CPh) CHPh} in good yield. The vinylic complex can also be obtained by reacting the sodio derivative of the chelating ligand with the 16e^– unsaturated complex, [Ru(CO)Cl(CH CHPh)(PPh₃)₂], in CH₂Cl₂/MeOH mixture at ambient temperature. These complexes have been characterized by elemental analyses, and i.r., ¹H, ¹³C and ³¹P n.m.r. spectroscopy.N.C.L Communication No. 5404.     

An <Emphasis Type="Italic">ab initio </Emphasis> Quantum-Chemical Study of C<Subscript>6</Subscript>H<Subscript>5</Subscript>S(O)CH<Subscript>3</Subscript> and C<Subscript>6</Subscript>H<Subscript>5</Subscript>S(O)CF<Subscript>3</Subscript>

The potential functions of internal rotation around the C -S bond in the C₆H₅S(O)CH₃ and C₆H₅S(O)CF₃ molecules were obtained by ab initio MP2(full)/6-31+G* calculations. The stationary points were identified by solving the vibrational problems. The structures in which the plane of the C -S-C bonds is approximately perpendicular to the benzene ring plane correspond to the energy minimum. The barriers to rotation around the C -S bond, corrected for the zero-point vibration energy, are 21.29 [C₆H₅S(O)CH₃] and 28.98 [C₆H₅S(O)CF₃] kJ mol⁻¹. The bond angles (deg) are as follows: 95.7 (CSC), 107.1 (C SO), 106.3 (C SO) in C₆H₅S(O)CH₃; 93.5 (CSC), 108.2 (C SO), 105.2 (C SO) in C₆H₅S(O)CF₃. The bond lengths are as follows (Å): 1.520 (S=O), 1.804 (C -S), 1.810 (C -S) in C₆H₅S(O)CH₃; 1.507 (S=O), 1.799 (C -S), 1.870 (C -S) in C₆H₅S(O)CF₃. According to the results of NBO calculations, the formally double S=O bond consists of a strongly polarized covalent σ bond (S→O) and an almost ionic bond. An increase in the S=O bond multiplicity relative to a single bond is mainly due to hyperconjugation by the mechanism n(O)→σ*(C -S) and n(O)→σ*(C -S) and, to a lesser extent, by interaction of the oxygen lone electron pairs with the Rydberg orbitals of the S atoms, characterized by a large contribution of the d component.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 1, 2005, pp. 96–104.Original Russian Text Copyright © 2005 by Bzhezovskii, Il’chenko, Chura, Gorb, Yagupol’skii.     

New Data on the Crystal Structures of Colusites and Arsenosulvanites

The crystal structures of three minerals (arsenosulvanite, V,As-germanite, and colusite) of the general crystal chemical formula (As, Ge, Sn, Sb, V)₆S₃₂, where Cu^M, V^M are cations at interstitial positions, 0.2 x 2.0, 2.7 y 0, (space group , a = 10.527; 10.600; 10.653 ; R = 0.066; 0.046; 0.033) have been determined using single-crystal X-ray diffraction data. The minerals are the two structural modifications of the compound with the ideal formula V₂Cu₂₄As₆S₃₂; they differ from each other in the occupancy of the interstitial position 2a. In colusite, this position is occupied by the V⁵⁺ cations; in arsenosulvanite and V,As-germanite, by Cu²⁺. A characteristic feature of the structures is the presence of octahedral [ S₄]Cu₆ ( = V, Cu) complexes not directly interacting with each other and lying inside the Laves polyhedra. In the structures of arsenosulvanite and V,As-germanite, a sulvanite framework consisting of interpenetrating Laves polyhedra T₃S₄ ( = V, Cu; T = Cu, As, Ge) has been found. The sulvanite framework is statistically distributed over the sphalerite matrix. The variable composition of the minerals is due to heterovalent isomorphism in the sphalerite position 6c. Charge disbalance arising from substitution of the pentavalent arsenic cations by cations of lower valence is compensated by the appearance of additional Cu²⁺ cations. The nonstoichiometry of the compositions is explained by the presence of vacancies in the interstitial and sphalerite positions.     

Stabilities in water and transfer activity coefficients from water to nonaqueous solvents of 15-crown-5 and 16-crown-5-metal ion complexes

Stability constants of 1 : 1 16-crown-5 (16C5)-metal ion complexes were determined in water at 25°C by conductometry and potentiometry with ion-selective electrodes. The selectivity sequences of 16C5 in water for univalent and bivalent metal ions are Ag⁺ > Na⁺ Tl⁺ > K⁺ and Sr²⁺ > Ba²⁺ Pb²⁺, respectively. The stability of a given 16C5-metal ion complex in water is much lower than might be expected on the basis of the solvation power (i.e. relative solubility of the metal ion) of water for the metal ion. The same tendency is observed for the cases of 15-crown-5 (15C5) -metal ion complexes. Transfer activity coefficients () of 15C5 and 16C5 for tetradecane (TD)/water, TD/methanol, TD/acetonitrile, and propylene carbonate/water systems were determined at 25°C. From these data, contributions of a methylene group and an ether oxygen atom to the log value of a crown ether were then obtained. The values from water to acetonitrile, propylene carbonate, and methanol of 15C5- and 16C5-univalent metal ion complexes were calculated, s, M⁺, and L being a solvent, a univalent metal ion, and a crown ether, respectively. The log value is greater than the corresponding log value. The log values are negative. This indicates that, although the M^- ions are more soluble in water than in the nonaqueous solvents, when the crown ether forms a complex with the M⁺ ion, the complex becomes more soluble in the nonaqueous solvents than in water, compared with the free crown ether. It was concluded from this finding that the unexpectedly low stability of the crown ether-M⁺ complex in water is attributed to strong hydrogen bonding between ether oxygen atoms of the free crown ether and water.     

About the stability of Au(NH3) 4 3+ in aqueous solution

The transformations of Au(OH) ₄ ^? in aqueous solutions (T = 20°C, I = 1) containing NH₃ and NH ₄ ⁺ (pH 8.1–8.5) were studied. The most pronounced changes in the system occur in the range 0 > log [NH ₄ ⁺ ] > ?2.0 (c _Au = (1?10) × 10^?4 mol/L, the monitoring time was about two weeks). When log [NH ₄ ⁺ ] > 0, Au(NH₃) ₄ ³⁺ dominates together with the amido form Au(NH₃)₃NH ₂ ²⁺ ; when log [NH ₄ ⁺ ] < ?2.0, no changes in the spectra are observed, probably, because of the very low rate of the processes. As c _Au increases in the indicated range, the polymerization rate grows. The equilibrium constant for Au(NH₃)₃OH²⁺ + NH₃ = Au(NH₃) ₄ ³⁺ + OH is log $ K_{4 OH, NH_3 } The transformations of Au(OH)₄⁻ in aqueous solutions (T = 20°C, I = 1) containing NH₃ and NH₄⁺ (pH 8.1–8.5) were studied. The most pronounced changes in the system occur in the range 0 > log [NH₄⁺] > −2.0 (c _Au = (1−10) × 10⁻⁴ mol/L, the monitoring time was about two weeks). When log [NH₄⁺] > 0, Au(NH₃)₄³⁺ dominates together with the amido form Au(NH₃)₃NH₂²⁺; when log [NH₄⁺] < −2.0, no changes in the spectra are observed, probably, because of the very low rate of the processes. As c _Au increases in the indicated range, the polymerization rate grows. The equilibrium constant for Au(NH₃)₃OH²⁺ + NH₃ = Au(NH₃)₄³⁺ + OH is log = −4.2 ± 0.3. This constant was used together with other constants, taking into account possible ligand effects, to estimate the formation constant of Au(NH₃)₄³⁺: logβ₄ = 47 ± 1, E _3/0 = 0.64 ± 0.02 V, log = −8.5 ± 1 (substitution of 4 NH₃ for 4 OH⁻ in Au(OH)₄⁻), log = 17.5 ± 1 (substitution of 4NH₃ for 4Cl⁻ in AuCl₄⁻). Original Russian Text ? I.V. Mironov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 4, pp. 711–715.     

Solubility of Oxygen in Some 1-1, 2-1, 1-2, and 2-2 Electrolytes as a Function of Concentration at 25°C

The solubility of oxygen has been measured in a number of electrolytes [(LiCl, KCl, RbCl, CsCl, NaF, NaBr, NaI, NaNO₃, KBr, KI, KNO₃, CaCl₂, SrCl₂, BaCl₂, Li₂SO₄, K₂SO₄, Mn(NO₃)₃)] as a function of concentration at 25°C. The solubilities, mol (kg-H₂O)^–1, have been fitted to a function of the molality m (standard deviation < 3mol-kg^–1)

Kinetics and mechanism of the acid-catalysed decarboxylation ofcis-[Co(cyclen)CO3]+

Summary The acid catalysed decarboxylation ofcis-[Co(cyclen)CO₃] has been studied over a range of nitric acid concentrations, at 25, 35.4 and 45°. The rate expression takes the form: k_obs=k₀+k₁ [H⁺], where k_obs is the observed first order rate constant at constant hydrogen ion concentration. The ko term which represents the spontaneous or water reaction is kinetically unimportant at the acidities used in the study. The activation parameters for the acid-catalysed decarboxylation are H=100.4 kj mol^–1 and S ₂₉₈=+51 JK^–1mol^–1. The acid catalysed reaction is subject to a deuterium solvent isotope effect consistent with a mechanism involving a rapid preequilibrium protonation of the complex followed by a slow ratedetermining ring opening of the carbonate ring.     

Proanthocyanidins ofPolygonum coriarium. IV. Structures of proanthocyanidins T3 and T4

Two oligomeric proanthocyanidins have been isolated from the roots ofPolygonum coriarium. By a study of their physical properties and spectral characteristics and analysis of the results of chemical transformations, the chemical structures of these compounds have been established as: (–)-epicatechin-77[O--D-glucopyranosyl]₃ O-⊃-D-glucopyranosyl (m-trigallolyl)-[(4-6)-(–)-epigallocatechin]₂-(4-6)-(–)-epigallocatechin—T3; and (–)-epicatechin-3-O-galloyl-7-[O--D-glucopyranosyl]₃O--D-glucopyranosyl galloyl-[(4-6)-(–)-epicatechin]₄-(4-6)-(–)-epigallocatechin — T4.The materials of this paper were presented at the IInd International Symposium on the Chemistry of Natural Compounds (SCNC), Eskiehir, Turkey, October 22–24, 1966).Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 707–713, September–October, 1997.     

Kinetics and mechanism of the displacement of aqua ligands from cis-diaqua-bis(biguanide)chromium(III) by pyridine-2-aldoxime in EtOH-H2O mixtures

Kinetic and mechanistic studies of the displacement of aqua ligands from cis-[Cr(BigH)₂(H₂O)₂]³⁺ (BigH = H₂NC(NH)CHC(NH)NH₂) by pyridine-2-aldoxime (LH) in EtOH-H₂O mixtures, in the 30–45° C range, obey the following rate law over the 3.5–6.0 pH range,

PbCu3(OH)(NO3)(SeO3)3·1/2H2O und Pb2Cu3O2(NO3)2(SeO3)2: Synthese und Kristallstrukturuntersuchung

Crystals of PbCu₃(OH)(NO₃)(SeO₃)₃·1/2H₂O [a=7.761(3)Å,b=9.478(4)Å,c=9.514(4)Å, =66.94(2)°, =69.83(2)°, =81.83(2)°, space group P ,Z=2] and Pb₂Cu₃O₂(NO₃)₂(SeO₃)₂ [a=5.884(2)Å,b=12.186(3)Å,c=19.371(4)Å, space group Cmc2₁,Z=4] were synthesized under hydrothermal conditions. Their crystal structures were refined with three-dimensional X-ray data toR _w=0.033 resp. 0.055. In PbCu₃(OH)(NO₃)(SeO₃)₃·1/2H₂O the Cu atoms are [4+1] and [4+2] coordinated and via SeO₃ groups a three-dimensional atomic arrangement is built up. In Pb₂Cu₃O₂(NO₃)₂(SeO₃)₂ there are sheets, which are connected only via Pb-O bonds ranging from 2.98 Å to 3.16 Å.

     

Solubility of Rhodochrosite (MnCO3) in NaCl Solutions

The solubility of rhodochrosite (MnCO₃) at 25°C under constant carbon dioxide partial pressure p(CO₂) was determined in NaCl solutions as a function of ionic strength I. The dissolution of MnCO₃(s) for the reaction

Establishment of The Power—Time Curve Equation of Bacterial Growth in the Log Phase

The power-time curves of two species of bacteria, Vibro metschnikovii, Vibro bollisae were determined calorimetrically by using a 2277 bioactivity monitor. The power-time curve equation of bacterial growth in the log phase can be expressed as

Kernquadrupolkopplung in einigen Kobalt(III)-komplexen

Zusammenfassung Aus Messungen der magnetischen Kernresonanz (MKR) an Einkristallen von [Co (NH₃)₅ H₂O] (ClO₄)₃ (I) und NH₄ [Co (NO₂)₄ (NH₃)₂] (II) wurden die Quadrupolkopplungskonstanten e ² Qq/h von Co⁵⁹ gewonnen. Ferner wurden die Linienbreiten der MKR in wÄ\rigen Lösungen von I, II und trans-[Co en₂Cl₂] Cl (III) gemessen.Aus e ² Qq/h und wurden nach der Theorie der Quadrupolrelaxation in Flüssigkeiten die Korrelationszeiten _cder Komplexionen bestimmt. Diese wiederum wurden zusammen mit den ebenfalls gemessenen Linienbreiten der MKR von N¹⁴ in wÄ\rigen Lösungen von I, II und III benutzt, um e ² Qq/h von N¹⁴ zu erhalten.Darüber hinaus wurden mittels geschÄtzter Korrelationszeiten und gemessener Linienbreiten der MKR von Co⁵⁹ und N¹⁴ für eine grö\ere Zahl von Co(III)-Komplexen NÄherungswerte von e ² Qq/h erhalten. Auf Grund dieser Werte wird die Elektronenstruktur der Komplexionen diskutiert.Die chemischen Verschiebungen der untersuchten Kernresonanzlinien werden angegeben. In einem Einkristall von I wurde die Anisotropie der chemischen Verschiebung bestimmt.

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Nuclear quadrupole coupling constants e ² Qq/h of Co⁵⁹ resulted from nuclear magnetic resonance (NMR) measurements on single crystals of [Co (NH₃)⁵ H₂O] (ClO₄)₃ (I) and NH₄ [Co (NO₂)₄ (NH₃)₂] (II). NMR line-widths were measured in aq. solutions of I, II, and trans-[Co en₂Cl₂] Cl (III). The correlation times _c of the complex ions resulted from e ² Qq/h and with the theory of quadrupole relaxation in liquids. These _c-values were used to obtain e ²Qq/h of N¹⁴ from NMR ine-width measurements of N¹⁴ in aq. solutions of I, II, and III.Approximate values for e ²Qq/h were obtained from NMR line-width measurements of Co⁵⁹ and N¹⁴ in a number of Co(III)-complexes with estimated correlation times. The electronic structure of the complex ions is discussed on the basis of the e ² Qq/h-values.The measured chemical shifts of the NMR-lines are listed. In a single crystal of I the anisotropy of chemical shift has been determined.

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Résumé Les constantes de couplage quadripolaire e ² Qq/h du ⁵⁹Co ont été tirées des mesures de la résonance nucléaire magnétique de monocristaux de [Co (NH₃)₅ H₂O] (ClO₄)₃ (I) et NH₄ [Co (NO₂)₄ (NH₃)₂] (II). En outre, la largeur des raies a été mesurée dans les solutions aqueuses de I, II et trans-[Co en₂ Cl₂] Cl (III).Les périodes de corrélation _c en ont été déduites d'après la théorie de la relaxation quadripolaire dans les liquides. Des _cet des du ¹⁴N, mesurés dans les solutions de I, II et III, on calcule e ² Qq/h pour ¹⁴N.Des _cestimés et de ⁵⁹Co et ¹⁴N mesurés pour plusieurs complexes du Co³⁺ s'obtiennent des valeurs approximatives de e ² Qq/h. Sur base de ces valeurs la structure électronique des ions complexes est discutée.Les déplacements chimiques (chemical shift) des raies de résonance examinées sont données. L'anisotropie du déplacement dans un monocristal de I a été déterminée.

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Herrn Professor Dr. P. Royen zum 60. Geburtstag gewidmet.