An NMR study of hydrogen exchange in p-hydroxybenzoic acid

The compound has been used over a temperature range in dimethylsulfoxide, with trichloroacetic acid and triethylamine as catalysts. The rate constant for uncatalyzed bimolecular exchange at 25 C is k_N=131 M^–1 sec^–1; the constant for acid-catalyzed exchange is k_A=0.9 · 10⁴ M^–1 sec^–1; and that for base-catalyzed exchange is k_B=0.5 · 10⁴ M^–1 sec^–1. The activation energy for uncatalyzed exchange is 5.75 kcal/mole. The exchange rates in dimethylformamide and acetone are higher, on account of differences in the hydrogen bond. The exchange rates of the isomers fall in the sequence ortho > para > meta, which is due to conjugation and intramolecular hydrogen bonding. The exchange mechanism is discussed. Simple relationships in dimensionless parameters are given for calculating the exchange rate from the shape of the NMR signal.     

Structure distortion effects in the spectrum of tunnel-exchange states of tetrahedral mixed-valence tetramers

Tunnel-exchange states of a tetrameric mixed-valence (MV) d₁–d₁–d₁–d₂ cluster are considered. Energy levels of distorted pseudotetrahedral conjiprations with rhombic and trigonal symmetry are calculated. It is demonstrated that the correlation diagrams of planar systems are symmetric with respect to the sign of the double exchange parameter. A strong double exchange always results in the ferromagnetic ground state of planar systems. The following types of spectrum defamations of the d₁–d₁–d₁–d₂ tetramer from tetrahedral to planar systems have been found: a) with a weak positive double exchange, deformation of a tetrahedral system does not lead to any change of spin of the antiferromagnetic ground state of the cluster; b) with a strong positive double exchange, the defonnation alters the antiferromagnetic ground (S = 1/2) state of the tetrahedral system to the ferromagnetic (S = 5/2) state of the planar system, or to an intermediate (S = 3/2) state; c) with a negative double exchange, irrespective of its absolute value, the tetrahedral system deformation does not alter the spin of the ground state. With a weak double exchange, this ground state remains antiferromagnetic, and with a strong double exchange, it is ferromagnetic or intermediate.Moldova State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 5, pp. 33–46, September–October, 1993.Translated by L. Chernomorskaya     

Physicochemical Study of New Mono- and Binuclear Copper(II) Complexes with Sterically Hindered Acylhydrazones and Azomethines

Series of new binuclear copper(II) complexes with acylhydrazones and azomethines of substituted derivatives of salicylaldehyde containing bulky tert-butyl substituents were synthesized. The target dimerization of the monomeric fragments of the complexes caused by the steric factors was shown to predetermine the specific features of their magnetochemical behavior. The calculated exchange parameters for the complexes based on acylhydrazones range from –110 to –138 cm^–1 and those for the complexes based on azomethines lie in the interval from –400 to –500 cm^–1.     

Ligand exchange reaction of Zn(II)-acetylacetonate complex with 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid

Ligand exchange reaction of Zn(II)-acetylacetonate complex (Zn-acac₂) with 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid (H₂TPPS) has been investigated spectrophotometrically and radiometrically. The exchange reaction was observed by spectral change from H₂TPPS to Zn-TPPS or activity of⁶⁵Zn(acac)₂ extracted into the chloroform phase. The 2nd order rate constants (k ₂) for the exchange reaction at 70 °C and at pH 7.8 were found to be 32.8±2.3 and 31.2±3.2 M^–1·s^–1 from the spectrometric and radiotracer experiments, respectively. For the direct complexation of Zn(II) with H₂TPPS, a similar 2nd order rate constant (k=32.4±4.7 M^–1·s^–1) was obtained as that in the ligand exchange reaction. The activation energies (E) for the exchange and the formation of Zn-TPPS were found to be 69.3±0.2 and 69.4±0.2 kJ·mol^–1, respectively, in the temperature range from 40 to 70 °C.     

Certain aspects of heterophase ion exchange

Ion exchange between an aqueous solution of KCl and a solution of tetraoctylammonium bromide in toluene has been studied at 20–70°C. Equilibrium exchange constants were measured. The free energy of the ion exchange is determined to a large extent by Coulombic interaction, which increases with decrease in the radius of the ion. The strength of the Q⁺X^– bond is weakened on passing from the normal onium salt to the hydrate and the rate of ion exchange increases. The position of equilibrium during approach to it from different sides may be affected by different formation processes of complexes with low activity in respect to exchange.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1773–1776, August, 1991.     

The unusual influence of the acidity of the medium on the rate of isotopic exchange of hydrogen of C6H6Cr(CO)2P(C6H5)3

Conclusions When the acidity function H₀ is varied from +1 to –2.5, the rate of the isotopic exchange of hydrogen of benzenechromiumdicarbonylphenylphosphine is directly proportional to the acidity of the medium, while in the case of higher acidities from –2.5 to –7.1, an inverse dependence is observed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 756–758, April, 1974.     

Hydrogen isotope exchange reaction rate in tritium and methane mixed gas

Hydrogen isotope exchange reaction rate in tritium and methane mixed gas, as induced by tritium decay and beta radiation, has been experimentally measured. Initially T₂ gas was filled to 40 kPa and 20 kPa of CH₄ gas was added. The mixed gas spectrum was analyzed periodically by laser Raman spectrometry. The first order HT and H₂ formation rates and T₂ and CH₄ decay rates by hydrogen isotope exchange reaction were observed between 2.9·10^–3 h^–1 and 4.8·10^–3 h^–1. Although the estimated hydrogen isotope exchange reaction rate was 1/20–1/10 slower than the rate of H₂+T₂ mixed gases, it was nearly equivalent to the ion formation rate by tritium beta radiation. This suggested that isotopic hydrogen radicals formed via ionization would disappear in the presence of methane.     

Sorption of cesium on montmorillonite and effects of salt concentration

The sorption behavior of cesium on montmorillonite type clay was studied by using radioactivity measurements. Concentrations of Cs⁺ ions ranged from 10^–6 to 10^–2M. Cesium retention reduced with increasing salt concentration which was varied between 10^–4 and 10^–1M. Selectivity coefficients K_Cs–Na for the exchange between Cs and Na were calculated for different equivalent fractions of Cs on the solid phase. Using theK _Cs–Na values, free energy change was found to be 7.8 kJ/mol. The data could be fitted to a Freundlich isotherm, and empirical Freundlich parameters enabled the generation of a site distribution function. By fitting the data to the Dubinin-Radushkevich (D-R) isotherm, a mean energy of sorption of 8.6 kJ/mole was calculated which corresponds to the energy of ion exchange reactions. The values of energy changes calculated by using two different methods were in good agreement.     

Isotopic Exchange and Oxygen Diffusion in the La0.88Sr0.12Ga0.82Mg0.18O3 – α–Molecular Oxygen System

The oxygen isotopic exchange kinetics in La_0.88Sr_0.12Ga_0.82Mg_0.18O_{3 –} and in the same electrolyte whose surface layer is enriched with cobalt ions is studied. Rates of different types of exchange and oxygen isotope diffusion coefficients in oxide are determined at 970–1200 K and oxygen pressures of 400–1200 Pa. The activation energy for the interphase oxygen exchange and the order of heteroexchange vs. oxygen pressure relationship are determined. The presence of cobalt ions in the near-surface layer alters the surface exchange parameters, such as the oxygen heteroexchange rate (which increases), order of the heteroexchange vs. oxygen pressure relationship, and the ratio between rates of different exchange types. The oxygen isotope diffusion coefficients coincide in both electrolytes but differ from those calculated from the electroconductivity data with the Nernst–Einstein equation.     

Investigation of the kinetics and equilibrium of the transfer of protons from dithiophosphoric acids to amines

The transfer of protons from dithiophosphoric acids R₂PSSH to substituted pyridines and proton exchange between the SH groups of the same acids and NH of protonated pyridines in chloroform solution were studied. The results obtained are compared with the analogous data for monothiocarboxylic acids RCOSH. The mechanism of SH-NH exchange was established; its slow step, just as for RCOSH, is transfer of a proton in the ion pairs. In the transition from RCOSH to R₂PSSH, an increase in the thermal effect of the deprotonation of the acids by amines and the activation energy E of SH-NH proton exchange is observed, which is due to the greater stability of the R₂PSS^– anions in comparison with RCOS^– on account of the greater delocalization of charge on the two sulfur atoms. With increasing excess of acid (above two-fold), the values of E are increased, since the excess acid molecules more effectively solvate the ion pairs than the original molecular complexes.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 6, pp. 676–681, November–December, 1985.     

An NMR study of proton exchange in the system p-nitrosophenol—p-quinone monooxime

The solvent used was dimethylformamide at neutral and alkaline pH. The equilibrium constants are determined by spectrophotometry. The rate of proton exchange has been measured as a function of temperature and concentration. The rate constants and activation energies have been measured; for uncatalyzed exchange k_n=(1.5±0.5) ·· 10³ M^–1 sec^–1, E=8±1 kcal/mole, while base-catalyzed exchange has k=(0.3±0.1) · 10⁶ M^–1 sec^–1 and E=6±1 kcal/mole.We are indebted to A. I. Brodskii for assistance in this work, and to V. I. Oshkaderov and L. A. Kichakova for recording the NMR spectra.     

Synthesis and magnetism of a binuclear copper(II)–manganese(II) complex with N,N-bis(N-hydroxyethylaminoethyl)oxamido as a bridging ligand

The heterobinuclear complex, [CuMn(L)(phen)2](ClO4)2· H2O, [L = N,N-bis(N-hydroxyethyleneamine)oxamido, phen=1,10-phenanthroline], has been synthesized with N,N-bis(N-hydroxyethylaminoethyl)oxamido as the bridging ligand. The electronic reflectance spectrum indicates the presence of exchange-coupling interaction between bridging MnII and CuII ions. The variable-temperature magnetic susceptibility of the complex was measured over the 4–300K range. The magnetic coupling parameter is consistent with an antiferromagnetic exchange between the MnII ion and CuII ion and fits the data for a heterobinuclear CuII–MnII magnetic exchange model based on the Hamiltonian operator (H= –2JS1S2, S1=1/2, S2=5/2), giving the antiferromagnetic coupling parameter of 2J=–74.0cm–1.     

Equilibrium of Br− and Cl− exchange on strong-basic anion-exchanger

The equilibrium of Br^– and Cl^– exchange is studied on the strong-basic anionexchangers. Quantitative characteristics which can be used for elaboration of dual-temperature separation processes have been obtained. An empirical equation for the dehydration extent of an anion in a phase of a sorbent has been suggested, allowing one to calculate the Br^– and Cl^– exchange equilibrium constants on the anion-exchanger in a wide temperature range.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2083–2089, December, 1994.     

Studies on ion exchange equilibria and kinetics VI. Prediction of ion exchange equilibria of UO 2 2+ −Na+−H+ ternary system

Experimental data are reported for the ion exchange equilibria of the binary systems UO ₂ ²⁺ –H⁺, UO ₂ ²⁺ –Na⁺ and Na⁺–H⁺, and of the ternary system UO ₂ ²⁺ –Na⁺–H⁺ on a strong acid cation exchange resin 001X7 at 25 °C. It is found that the equilibria for any pairs of ions are essentially the same in binary and ternary mixtures and that the prediction method proposed by our laboratory for SO ₂ ^2– –Cl^––NO ₃ ^– -201X7 strong base anion exchange resin system is also applicable to the ternary system studied in this paper. The predictions of the ternary system UO ₂ ²⁺ –Na⁺–H⁺ based solely on the binary data without using resin phase activity coefficients are consistent with the experimental data.     

A method for the determination of the uranium content in U-Al alloys

The paper describes a method for the determination of uranium content in enriched U–Al alloys. The mass-spectrometric isotope dilution method was proposed and verified for the determination of uranium in these materials. A solution of natural uranylnitrate, prepared by dissolution of standard reference material NBS-U-960, was used as a spike. Uranium was separated from aluminium in the form of chloro complexes by sorption on anion exchange resin Dowex 1-X8 from 9M HCl. The error of determination lies in an interval 0.03–0.07% rel. for uranium contents 18.2–22.8 wt%.     

Sorption of nickel on marl

Batch sorption experiments using nickel have been carried out on marl, a sedimentary, carbonaceous rock. All experiments were performed with a synthetic water of pH 7.3 and in an atmosphere of N₂/1% CO₂. Over the equilibrium nickel concentration range of 10^–11–10^–5M, sorption was linear and reversible with R_d of 819 ml g^–1. Owing to the linear sorption behavior, R_d was independent of rock/water ratio (r/w=1/5–1/100). The data suggested that at [Ni] lower than 10^–7M an isotope exchange mechanism operated, whereas at higher [Ni], sorption involved ion exchange. Sorption experiments on some of the components of marl indicated that nickel adsorbs mainly on the clay minerals and on the trace of iron hydroxide present; sorption on calcite and quartz was low.     

Reaction of perfluoroalkyltriazines with amidines of perfluoroalkylcarboxylic acids

Conclusions The amidines of perfluorocarboxylic acids and perfluorotriazines enter into exchange reaction at 20–60° to give an equilibrium mixture with new triazines and amidines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1118–1121, May, 1979.     

The first oxalato-bridged dinuclear CoII–VIVO complexes: synthesis and magnetism

Two novel CoII–VIVO oxalato complexes have been synthesized and characterized, namely [CoL2VO(OX)2·3H2O [L = 1,10-phenanthroline (phen) or 2,2-bipyridyl (bipy), OX = oxalate dianion]. Based on i.r. and electronic spectra and elemental analyses, extended oxalato-bridged structures consisting of VO2+ and CoII species, in which each VIV has a distorted square pyramidal environment and each CoII has a distorted octahedral environment are proposed for the two complexes. The temperature dependence of the magnetic susceptibility for [CoL2VO(OX)2]·3H2O (L = phen, bipy) was measured over the 77–300 K range and the observed data were successfully simulated by an equation based on the spin Hamiltonian operator H^=–2JS^1S^2 giving the exchange integral J=–62.5 cm–1 and J=–40.3 cm–1 for the phen and bipy complexes, respectively. These indicate antiferromagnetic spin exchange interaction between the CoII and VO2+ centres.     

Modes of137Cs desorption from marine sediments by sea water

Sea water is observed to be a good desorbing agent for¹³⁷Cs from marine sediments. Investigations on the sites of¹³⁷Cs binding and their abundance by desorption over extended periods indicated that, whatever the time of contact of sorption,¹³⁷Cs has three modes of desorption: fast component with desorption half-time of 30–50 min, medium component with desorption half-time of 25–50 h and slow component with desorption half-time of 31–112 days. These are expected to be sites of ion exchange, slower exchange and trapped Cs in the clay mineral layer lattices.     

Vibronic reduction of Heisenberg and double exchange in multielectron mixed-valency clusters

Vibronic reduction is considered for Coulomb interaction between centers for Heisenberg and double exchange in multielectron mixed-valency d²-d³ clusters. A simplified multimode vibration model indicates how effects arise via vibrations from the correlation interaction between electron shells. Vibronic reduction in double exchange can alter the magnetic parameters for the cluster's ground state.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 2, pp. 114–121, March–April, 1992.