Thermodynamic quantities for the interaction of SO 4 2− with H+ and Na+ in aqueous solution from 150 to 320°C

The aqueous reactions,

Komplexverbindungen von Germaniumsäure mit ÄDTE und ÄDTE-Analogen, 1. Mitt.: Äthylendiamintetraessigsäure

Zusammenfassung Die Verbindung GeY · 2 H₂O wird nach einem Verfahren dargestellt, das die Verwendung von flüchtigem GeCl₄ vermeidet und direkt von Germaniumsäure-Lösungen ausgeht. Der Komplex, der analysenrein anfällt, wird thermogravimetrisch untersucht. In Wasser gelöst, erweist er sich als einbasige Säure, H[Ge(OH)Y]. Die Dissoziationskonstante der komplexen Säure wird potentiometrisch bestimmt:K _c =3,99 · 10^–3 (pK _c =2,40). Die Stabilitätskonstanten der komplexen Säure sowie des komplexen Anions werden ermittelt: =6,27 · 10⁴ (log =4,80); =3,34 · 10⁴ (log =4,52) (25°C; Ionenstärke 0,1m).

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The complex compound GeY · 2 H₂O is prepared directly from germanic acid solutions, avoiding volatile GeCl₄. It has been submitted to thermogravimetric analysis. Dissolved in water, it proves to be a monobasic acid, H[Ge(OH)Y]. The dissoziation constant of the complex acid is determined potentiometrically:K _c =3,99 · 10^–3 (pK _c =2,40). The stability constants of the complex acid as well as of the complex anion are evaluated: =6,27 · 10⁴ (log =4,80); =3,34 · 10⁴ (log =4,52), at 25°C; ionic strength 0,1m.

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Mit 4 Abbildungen

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Herrn Prof. Dr.J. W. Breitenbach zum 60. Geburtstag gewidmet.     

The Energy of Interaction between Water Monolayer and Carbon Surface and the Determination of H-Bond Energy from the Isotherms of Water Desorption by Organic Molecules into an Aqueous Solution

It is proven that, when passing from a liquid into an adsorption phase on a carbon surface, the maximal number of H-bonds between water molecules decreases from four to three because of the screening of one unpaired electron of the oxygen atom of an adsorbed water molecule by aromatic rings of the carbon surface. An energy gain equal to the energy of one H-bond arises upon water desorption by organic molecules adsorbed from an aqueous solution. The ratio between the number of H-bonds of a group of water molecules, which is displaced into a solution by one organic molecule, in the solution and in the adsorption phase is independent of the number of molecules in this group and is, on the average, equal to 2.038 for all possible structures of H-bonds in both phases. The allowance for this ratio in the isotherm of water desorption into a solution and the introduction of a coefficient, which depends on the relative water content ( ) in the adsorption phase, in the form of into the equation of the desorption isotherm make it possible to determine the balance of the change in the Gibbs energy at the desorption equilibrium and the standard Gibbs energy = –1.76 kJ/mol of water desorption into a solution from a carbon surface. This value determined by an independent method is = –1.79 kJ/mol; i.e., both values are close to each other. The RTlnf energy of the additional H-bond, which is formed between water molecules upon passing from the adsorption phase into the solution, is found by the extrapolation of the isotherms of water desorption by molecules of several benzene derivatives. This energy ranges from 9.13 to 9.24 kJ/mol, thus corresponding to the energy of one H-bond, as measured by IR spectroscopy and NMR.     

Kinetics and mechanism of anation of hexaaquochromium(III) by 2-aminopyridine

The kinetics of substitution of aqua ligands from the hexaaquochromium(III) ion by 2-aminopyridine (2-ampyH⁺) in aqueous medium has been studied spectrophotometrically in the 40–55° C range. The rate law involving the outer sphere complex formation has been established at pH 2.7 as

Reactions of alkoxy and hydroxy radicals generated photochemically from hydroperoxide molecules

In the present work as well as HRO^. radicals were generated in the photochemical interaction of 1,2-benzanthracene with -ethyl phenyl hydroperoxide /HROOH/ in C₆H₆ and CCl₄ at 304 K. radicals were trapped by C₆H₆. The main reaction of HRO^. radicals is hydrogen abstraction from the hydroperoxide group of HROOH. Although OH radicals are less selective, the hydrogen abstraction is the main process during their interaction with aromatics in contrast to reactions in aqueous solutions, where addition to the benzene ring is the rate-determining process in CCl₄:

A comparative kinetic and mechanistic study of glutamic acid oxidation by acid permanganate in the absence and presence of sodium dodecyl sulphate

The kinetics and mechanism of glutamic acid (GCO₂H) oxidation by acid permanganate has been carried out in the absence and presence of sodium dodecyl sulphate (SDS). The surfactant enhances the reaction rate without changing the reaction mechanism. The overall rate expression for the reduction of Mn^VII may be written:

Complexation of aluminate anion by bis-tris in aqueous media at 25–50°C

Gibbsite, Al(OH)₃, solubility studies in aqueous NaCl solutions at pH 9 demonstrate that the aluminate anion forms a strong complex with the neutral Bis-tris molecule 2,2-Bis(hydroxymethyl)-2,2,2-nitrilotriethanol, at low temperatures. The logarithm of the molal concentration quotient for the reaction

Kinetic study of hydrogen peroxide reaction with hydroxonitrilotri(methylenephosphonato)iron(III) complex

The decomposition of hydrogen peroxide in the presence of hydroxonitrilotri(methylenephosphonato)iron(III), [Fe(NTMP)(OH)^4–], was studied in nitrate media (=0.10–0.26 M) over the 0.2–0.5 mM concentration range for the iron complex and the temperature range 26–40°C. The rate law;

Trace metal ion catalysis; kinetics and mechanism of oxidation of metol by hydrogen peroxide in the presence of iron(III) sulphate in acid perchlorate

The kinetics of oxidation of N-methyl-p-aminophenol (metol) by H₂O₂ in the presence of trace levels of Fe^III have been studied in an HClO₄ medium. The reaction mechanism is complex and the catalytic role of Fe^III in the sulphato form is indicated. The following rate law accounts for the experimental observations:

Formation of Tc(III)-EDTA complex

Tc(III)-EDTA complex has been synthesized by the ligand substitution reaction of hexakis-(thiourea) technetium(III) ion with EDTA. The complex exhibits absorption maxima at 368 and 470 nm. The formation reaction proceeds predominantly as follows:

The partial molal volume and compressibility change for the formation of the calcium sulfate ion pair at 25°C

The apparent molal volumes (_v) and compressibilities (_K) of CaSO₄ solutions have been determined at 25°C from precise density and sound-speed measurements. The large deviations of the values of _v and _K from the limiting law and various additivity estimates for the free ions (Ca²⁺, SO ₄ ^2– ) have been used to estimate the partial molal volume ( ) and compressibility ( ) for the formation of the CaSO ₄ ⁰ ion pair. Values of = 25 ± 3 cm³-mole^–1 and = (54±21)×10^–4 cm³-mole^–1-bar^–1 were found. Since these values are larger than the value for the formation of MgSO ₄ ⁰ , the results indicate that more inner-sphere ion pairs are formed when SO ₄ ^2– complexes with Ca²⁺ than with Mg²⁺. Using a simple model for ion-water interactions, the percent of inner-sphere or contact ion pairs in CaSO₄ solutions is estimated to be 36 to 37%.     

Some analytical results forABC,ABCD, andXBCD coupled spin 1/2 systems. II

In the preceding paper, it was shown that the calculation of the density matrix(t) for multiply connectedABC, etc., spin 1/2 spin systems can be greatly simplified by subdividing the Hamiltonian into , where is a suitable linear combination of the constants of the motion. In this paper, a framework for the determination of the time evolution of high-order multipolar quantum states is presented and discussed. It is shown that the necessary mathematical labour is reduced to a minimum by (i) exploiting the fact that is a good quantum number, and (ii) using the theory of partitioned matrices. For example, it is shown that for a generaln-coupled spin 1/2 system, the spin dynamics of the multipolar states, whereK _max is the maximum tensorial rank, can be determined without the need to diagonalize the full 2 ⁿ × 2 ⁿ Hamiltonian matrix, wheren is the number of spins. In fact, to describe the time evolution of the multipolar states it is only necessary to diagonalize twon ×n matrices at most. Finally, some cautionary remarks are made concerning the use of the weak-coupling approximation.     

Extent of exchange of bromine-82 with bromamine-T in strong acid medium

The extent of exchange of bromine-82 with bromamine-T in strong acid medium is low due to the formation of at lower acid concentrations and bromine at higher acidities. formation occurs over a narrow acid concentration range and is less stable than .     

Solvent effects on the anation ofcis-diaquo-bis-ethylenediamine cobalt(III) by L-proline

The anation kinetics of the title complex were investigated spectrophotometrically in aqueous methanol, ethanol, ipropanol, t-butanol and dioxane, and the following rate law was established:

Osmium liquid-phase catalysts for hydrogenolysis of saturated hydrocarbons and hydrogenation of arenes

Reduction of OsO₄ by molecular hydrogen in alkane (cycloalkane) or benzene (toluene) solution produces small-ligand clusters of osmium of composition Os_1.5–2.5. CH_0–2 with a particle size 10–40 Å and a specific surface area of 34–46 m²/g. Hydrogenation of dry catalyst produces methane. The small-ligand osmium clusters obtained effectively catalyze hydrogenolysis of alkanes and cycloalkanes at 100–150°C and =5 MPa and hydrogenation of benzene at 20°C and =0.1 MPa.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2428–2433, November, 1989.     

A generalized separation reaction scheme for assessment of the radioanalytical method of concentration dependent distribution

For the assessment of the analytical error of concentration dependent distribution (CDD), complex-forming separation reaction was proposed in a generalized form of equilibrium , where n is the effective stoichiometric coefficient, i.e. the difference of mean ligand numbers and <n> of a mixture of complexes of analyte M with reagent L in the respective groups (distinguished by bars above the symbols) of the separation system. Calibration curve is derived from measurement of gross activity of complexes, A=A(ML_<n>) and . Theoretical relative error is expressed as a product of three terms, x/x=f₁f₂f₃. The first term f₁ depends on the degree of isotopic dilution, and the recommended ratio of amounts of nonradioactive (x) and radioactive (y) substance M is x/y(1;4). The second term f₂ depends first of all on the slope of distribution ratio (yield of separation ) vs. the analyte; reagent ratio, n(Z+1)/T. The form of slope is analyzed on the basis of the generalized separation reaction. Optimal conditions were discussed from this point of view and the ideal case is at f₂=1. The third term f₃ depends on the activities A and , i.e. on the distribution ratio, sample volumes, and the manner of counting. The ideal ratio of sample activities is A= and the optimal interval (0.2;0.8) is suggested     

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.     

Some analytical results forABC,ABCD, andXBCD coupled spin 1/2 systems. I

By choosing a suitable linear combination of the constants of the motion , it is shown that the calculation of the density matrix(t) can be simplified by subdividing the Hamiltonian into . In particular, this technique can be used to obtain closed form solutions for the eigenfunctions and eigenvalues of spin 1/2ABC andXBCD spin systems, evolving in the presence of Zeeman offsets, scalar coupling and dipolar interactions. In general, the eigenvalues and eigenvalues of are very transparent, while those of require more effort. Nevertheless, simplifications can be made. Firstly, the effective size of the Hamiltonian matrix which needs to be considered, is reduced fromN ×N to at least (N – 2) × (N – 2), while forXBC ... systems it is reduced to (N – 4) × (N – 4). Secondly, the highest rank and highest/lowest order tensor operators available to the spin ensemble are constants of the motion under . Finally, by exploiting the fact that is a good quantum number, it is possible to block-diagonalize the matrix into no more than 3 × 3 matrices.     

Phosphororganische Verbindungen, 6. Mitt. Oxydation von β-Ketophosphoniumsalzen und Alkylenphosphoranen mit Äthylnitrit

Zusammenfassung -Ketophosphoniumsalze der allgemeinen Struktur können mit Alkylnitriten zu Triphenylphosphinoxid und -Ketonitrilen RCOCN oxydiert werden. Ähnlich werden Alkylenphosphorane A umgesetzt: Für R₁=H, R₂=Alkyl entstehen Nitrile, während für R₁=Alkyl, R₂=Alkyl Ketoximäther gebildet werden.

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-Ketophopshonium salts of the general structure can be oxidized by alkylnitrites to form triphenylphosphinoxid and -ketomitriles. Alkylenphosphoranes triphenylphosphinoxid and -ketonitriles. Alkylenphosphoranes (A) can be oxidized in the same manner. For R₁=H, R₂=alkyl the reaction product is nitrile whereas for R₁=alkyl, R₂-alkyl the products are ketoxime ethers.

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Mitt.:E. Zbiral, Mh. Chem.96, 1967 (1965).     

The Hydrolysis of Protactinium(V) Studied by Capillary Diffusion

The mean diffusion coefficient of ²³³Pa has been measured simultaneously with those of ²²Na and ¹⁵²Eu in 0.5 M (Na, H)ClO₄ solutions with the pH ranging from 0.3 to 13, by the open-end capillary method optimized in order to obtain reproducible and reliable D values at T = 25°C. In the case of Eu(III), the results tend to give higher ₁₃ and ₁₄ hydrolysis constants than the values generally acccepted, but these data are probably affected by the formation of polynuclear or colloidal species as soon as the hydrolysis process is involved. For Pa(V), results are in agreement with the existence of the following two equilibria (I = 0.5 M, T = 25°C):