A study of the behavior of cadmium and zinc microquantities in sorption and coprecipitation processes in tetrahydrofuran solutions

The sorption of ¹⁰⁹Cd and ⁶⁵Zn microquantities with NaX and NaA zeolites in the presence of divalent lanthanides (Ln²⁺) (Ln=Tm, Dy, and Nd) from tetrahydrofuran (THF) solutions was studied. It was found that in contrast to ¹³⁷Cs⁺, ¹⁰⁹Cd and ⁶⁵Zn, as well as ⁸⁵Sr²⁺ microquantities were sorbed by zeolites very poorly: ∼99% of the species remained in solution. The distribution coefficients (K _d ) of ¹⁰⁹Cd and ⁶⁵Zn were ∼0.3 and ∼0.4 ml/g, respectively. When Tm²⁺ was used as a reducer, it partially oxidized in solution to Tm³⁺ to form precipitates of the composition TmI₃·3THF. A study of the co-crystallization of ¹⁰⁹Cd and ⁶⁵Zn, as well as ⁸⁵Sr²⁺ microquantities with the TmI₃·3THF solid phase in the presence of Tm²⁺ from THF solutions showed that in contrast to ⁸⁵Sr²⁺, ¹⁰⁹Cd and ⁶⁵Zn microquantities co-crystallized with the TmI₃·3THF solid phase. The co-crystallization coefficients (D) for ¹⁰⁹Cd and ⁶⁵Zn depended on the ratio Tm³⁺/Tm²⁺ in solution and increased with its increasing. The assumption was made that in the presence of Tm²⁺, ¹⁰⁹Cd²⁺ and ⁶⁵Zn²⁺ form M⁺ ions, which quickly react with M²⁺ ions to form dimers of the composition M₂ ³⁺ (M=Cd and Zn).     

501—An electrochemical study of energy-dependent potassium accumulation in E. coli: Part IX. Reversal of the mechanism exchanging 2 H+ for K+ with the coupled synthesis of ATP

E. coli is able to exchange 2 H⁺ from the external medium for one K⁺ of a cell with the concurrent synthesis of ATP. The 2 H⁺/K⁺ exchange and the coupled ATP synthesis are in need of both the essential Δ$\text{}\text{?}$gm_H+ (around 24 kJ) and the high K⁺ gradient (10³) directed from a cell to the medium. The reverse pump cycle is actuated as well as the direct one [3] merely through an increase of osmolarity in the environmental medium. The reverse process can be blocked by the insignificant ncrease in external pH or in K⁺ concentration, as well as by DCCD or by protonophore. The stoichiometry of the entire pump cycle is ATP: 2 H⁺ :K⁺. These observations, as well as the previous findings [8,9] that 2 H⁺ from a cell and one external K⁺ are transported through F₁·F₀ and TrkA respectively, suggest that F₁·F₀ and TrkA form the structural association in bacterial membrane for the joint employment of phosphate bond energy, the supercomplex (F₁ ·F₀TrkA operating as an electrogenic proton-potassium pump with stable stoichiometry ATP:2 H⁺ :K⁺.     

Characterization of an Irish Sea radioactively contaminated marine sediment core by radiometric and mass spectrometric techniques

Summary A radioactively contaminated marine sediment core stemming from Irish Sea has been characterized by radiometric and mass spectrometric techniques as for ²³⁷Np, ²⁴¹Am, ²³⁹Pu, ²⁴⁰Pu, ²⁴¹Pu, ¹³⁷Cs and ¹⁵⁴Eu. The data obtained with independent methods in the framework of a QA/QC program as compared with the source term discharges, as well as with those reported in literature, are in good agreement.     

Theoretical study of the N+2 molecular ion

The Equations of Motion method has been applied in the calculation of potential energy curves for the X²Σ⁺_g, A²Π_u and B²Σ⁺_u states of N⁺₂. Results are also reported for a new dissociative ²Σ⁺_g state. The theoretical curves are directly compared with the experimental ones as well as in terms of spectroscopic constants. The applicability of the Equations of Motion method to this type of problem is critically examined and discussed with regard to the choice of basis set, numerical effort and agreement with experiment.     

195Pt NMR of organoplatinum compounds

The ¹⁹⁵Pt chemical shifts of several organoplatinum compounds in solution have been determined. The δ(¹⁹⁵Pt) values of the phosphine-Pt^II and -Pt⁰ compounds lie in separate ranges, and allow the metal-diene systems to be characterized either as metallacyclopentene or as η²-bonded diene. Although the two isomers of bis(η³-allyl)Pt (VIII) formally should be regarded as Pt^II compounds their ¹⁹⁵Pt shifts clearly lie in the region for Pt⁰ compounds. The large separation between the ¹⁹⁵Pt signals and the difference in ¹⁹⁵Pt-T₁ values for the two isomers of VIII are in accord with their having different geometries around the metal.     

239+240Pu concentrations of sediments and seawater in the coastal sea of Korea

Summary The ^239+240Pu content of the marine sediments and seawater of the costal sea of Korea was measured. In marine sediments the ^239+240Pu concentrations were in the range of 0.11-1.91 Bq/kg dry weight and in the coastal sea of Korea the ratio of ^239+240Pu/¹³⁷Cs was 0.27. The correlations between ^239+240Pu and ¹³⁷Cs concentrations and the content of organic matter (C, O, H, N, S) as well as the grain size of marine sediment were investigated by regression analysis. The distribution coefficient of ^239+240Pu was 1.22^. 10⁵. The ^239+240Pu concentration in seawater increased with seawater depth. However, the ¹³⁷Cs concentration in seawater did not change considerably with depth.     

Volumes of mixing and theP * effect: Part II. Mixtures of alkanes with liquids of different internal pressures

The Flory theory of solution thermodynamics is used to predict exess volumes for systems containing a series of n-alkanes mixed with liquids of higher P^* parameter and internal pressure, i.e., cyclopentane, cyclohexane, carbon tetrachloride, benzene and dioxane as well as of lower P^*, i.e., decamethyltetrasiloxane. Trends of V ^E , e.g. changes of sign with alkane carbon number are well predicted and indicate the importance of the P^* contribution in V ^E . Mixtures of hexane isomers with liquids of much higher P^* typically have large excess enthalpies through zero as an S-shaped curve against composition which is negative on the side of the high P^* component. This behaviour is interpreted as arising from increasingly large negative P^* contributions in V ^E .     

Thermodynamic study of the interaction of Co(II)-Schiff base complexes with phosphines

The equilibrium constants and the thermodynamic parameters for the interaction of CoL^x (L¹ = 5-OMe-salabza, L² = salabza, L³ = 5-Br-salabza and L⁴ = 5-NO₂-salabza) as acceptors, with phosphines (PBu₃, PPh₂Me) as donors in dichloromethane were studied. This was performed by using UV-Vis spectrophotometry titration for 1:1 adduct formation of the selected complexes at various temperatures (T = 283–298 K). The trend of the adduct formation of the Co(II) complexes with a given phosphine donor decreases as CoL¹ > CoL² > CoL³ > CoL⁴. The stability of the resulting adducts with different Co(II)-schiff base complexes found to decrease in the order PBu₃ > PPh₂Me.     

Evaluation of methane negative ion chemical ionization mass spectra of polycyclic aromatic hydrocarbons and related compounds

Negative ion chemical ionization (NICI) mass spectra with methane as reagent gas and the ion abundance ratios of the negative to the positive base peak for 51 polycyclic aromatic hydrocarbons and related compounds were measured and evaluated for highly sensitive detection and isomer differentiation. Either [M ? H]^?, M^?˙ or MH^? was the base peak, except for one compound with [M ? H₂]^?˙ as its base peak. The numbers of compounds with [M ? H]^?, M^?˙ or MH^? as their base peaks were 17, 26 and 7, respectively. Many of the compounds with [M ? H]^? as the base peak had an aliphatic part in their structure. The average value of N/P (negative/positive ion abundance ratio at the base peaks) was < 1. Many of the compounds with M^?˙ as the base peak had a relatively high electron affinity. A correlation between electron affinities and ion abundances was found. In most cases, the N/P ratios were > 1, and even reached 400 in benzo [a] pyrene. Many of the compounds with MH^? as their base peaks had a phenyl group, in which cases the N/P ratios were < 1. In the case of compounds with 18 or fewer carbon atoms, in particular, it was easy to distinguish isomers by comparing their NICI mass spectra. The N/P values served as a guideline in sensitive detection. Nine compounds achieved an N/P of ≥50.     

Influence of natural sorbents on the immobilization of spent ion exchange resins in cement

Summary Leach characteristics of ¹³⁷Cs and ⁶⁰Co radionuclides from spent mix bead ion exchange resins and both ordinary Portland cement and cement mixed with two kind of natural sorbents (bentonite and clinoptilolite) have been studied using the International Atomic Energy's (IAEA) standard leach method. The waste immobilization performance of low-level wastes in natural sorbent mixtures was determined. The solidification matrix was a standard Portland cement mixed with 290-350 (kg/m³) spent mix bead exchange resins, with or without 1-10% of bentonite or/and clinoptilolite. The leaching rates from the cement-bentonite matrix were measured after 300 days as ⁶⁰Co: (1.20-9.72) ^. 10^-5 cm/d and ¹³⁷Cs: (1.00-9.22) ^. 10^-4 cm/d. From the leaching data, the apparent diffusivity of cobalt and cesium in cement-bentonite or/and clinoptilolite matrix with a waste load of 350 kg/m³ of spent mix bead exchange resin was calculated as ⁶⁰Co: (1.0-5.9) ^. 10^-6 cm²/d and ¹³⁷Cs: (0.48-2.4) ^. 10^-4 cm²/d. The compressive strength of these samples is determined according to the ASTM standards.     

Isolation of137Cs from excreta by dicarbolide of cobalt

Extraction by polyhedral complex compound of the formula H⁺ [(π-(3)-1,2-B₉C₂H₁₁)₂Co⁻] further on referred to as dicarbolide-H⁺ and its chloro-derivate H⁺[B₁₈C₄H₁₅Cl₇Co⁻] further on referred to as Cl-dicarbolide-H⁺ in nitrobenzene was used for the analysis of¹³⁷Cs in urine and faeces after internal contamination. The dependence of distribution ratio on the acidity of analysed solutions was determined. The effect of urine dilution was assessed as well as the effect of various concentrations of the extraction agents on the distribution ratio of¹³⁷Cs. The effect of phase ratio at the different concentrations of isotopic carrier was assessed, as well as the effect of potassium ions on the decrease of the distribution ratio at the extraction of¹³⁷Cs by dicarbolide-H⁺ or its chloro-derivate. The possibility of isolation of¹³⁷Cs by extraction and the isolation of¹³⁷Cs by ion-exchange absorbents and by ammonium molybdophosphate was compared. The values of distribution coefficient were determined at various concentrations of nitric acid and the isotopic carrier. The dependence of coextraction of some activated radionuclides and fission products by dicarbolide-H⁺ on the nitric acid concentration in the solute was determined. The effect of mass of contaminated faeces on the value of the distribution ratio of¹³⁷Cs by the extraction was evaluated. As a result, a suggestion was given for the rutine isolation procedure of¹³⁷Cs extraction with dicarbolide-H⁺ from the excreta contaminated by a mixture of radionuclides.     

133Cs NMR Spectroscopic Investigation of the Interaction of 133Cs+ with Monovalent Cations in Aqueous Solution

¹³³Cs NMR spectroscopy was used to study the interaction of ¹³³Cs⁺ with monovalent cations in aqueous solution. The interaction between ¹³³Cs⁺ and the cations causes a repulsive polarization in the electron environment of ¹³³Cs⁺, which is detected by a change in its resonance frequency. The resulting ¹³³Cs chemical shift seemed to be dependent on the activities and the single-ion enthalpies and entropies of hydration of the cations. The hydration cospheres of an ion are the barriers through which ¹³³Cs⁺ must pass in order to come into contact with the cation. These hydration cosphere barriers can be related to the single-ion enthalpy and entropy of hydration of the cation. The experiments revealed that ¹³³Cs⁺ is not nearly as sensitive a probe as ¹²⁹Xe, presumably due to its more tightly bound hydration cospheres. However, ¹³³Cs NMR was moderately successful in predicting trends in the chemical shift behavior induced by the cations studied.     

Effect of gamma and electron-beam irradiation on the anisotropy of electric properties of indium selenide

The generation and distribution of radiation defects in single-crystal samples of indium selenide with an electron number density of 5 × 10¹⁴−1 × 10¹⁶ cm⁻³ during irradiation with γ-rays (doses of 10⁷ and 10⁸ R) and 25-MeV electrons (fluences of 10¹⁵ particle/cm²) was studied, as well as the behavior of the mobility.     

The diffusion of H+ and Ni2+ ions in an inorganic cation-exchange matrix

The kinetics of sorption on zirconium hydrophosphates with various water contents was studied. The self-diffusion coefficients of Ni²⁺ and H⁺ and the effective diffusion coefficients of Ni²⁺ ions corresponding to the exchange Ni²⁺ → H⁺ were determined. The self-diffusion coefficients of ions in samples with an 85% water content were as high as 4.17 × 10^?11 m²/s (Ni²⁺) and 5.06 × 10^?10 m²/s (H⁺). Water loss caused by drying the sorbents resulted in a decrease in the rate of ion exchange.     

Determination of Sulfur Compounds in Water Samples by Ion Chromatography Dynamic Reaction Cell Inductively Coupled Plasma Mass Spectrometry

An ion chromatography‐inductively coupled plasma mass spectrometric (IC‐ICP‐MS) method for the speciation of sulfur compounds, namely sulfite [SO₃^2?], sulfate [SO₄^2?] and thiosulfate [S₂O₃^2?], was described. Ionic sulfur compounds were well separated in about 3 min by ion chromatography with a Hamilton PRP‐X100 column as the stationary phase and 60 mmol L^?1 NH₄NO₃ and 0.1% v/v formaldehyde (HCHO) solution (pH = 7) as the mobile phase. The analyses were carried out using dynamic reaction cell (DRC) ICP‐MS. The sulfur‐selective chromatogram was determined at m/z 48 as ³²S¹⁶O⁺ by using its reaction with O₂ in the reaction cell. The method avoided the effect of polyatomic isobaric interferences at m/z 32 caused by ¹⁶O¹⁶O⁺ and ¹⁴N¹⁸O⁺ on ³²S⁺ by detecting ³²S⁺ as the oxide ion ³²S¹⁶O⁺ at m/z 48, which is less interfered. The detection limit of various species studied was in the range of 3.6–4.6 ng S mL^?1. The accuracy of the method has been verified by comparing the sum of the concentrations of individual sulfur compounds obtained by the present procedure with the total concentration of sulfur in several natural water samples. The recovery was in the range of 97–102% for various compounds studied.     

Kinetic study on reactive extraction for chiral separation of phenylsuccinic acid enantiomers

The kinetics of the extraction of phenylsuccinic acid (PSA) enantiomers by hydroxypropyl-β-cyclodextrin (HP-β-CD) in a modified Lewis cell was studied, in which HP-β-CD dissolved in 0.1 mol L^?1 NaH₂PO₄/H₃PO₄ buffer solution (pH = 2.5) was selected as the chiral extractant. PSA enantiomers were extracted from organic phase to aqueous phase in the extraction module. The theory of extraction accompanied by a chemical reaction has been used to obtain the intrinsic kinetics of this extraction module. The different parameters affecting the extraction rate such as agitation speed, interfacial area, initial concentration of PSA enantiomers in organic phase as well as HP-β-CD concentration in aqueous phase were separately studied. The experimental results demonstrate that the extraction reactions are fast. The reactions were found to be first order with respect to PSA and second order with respect to HP-β-CD with forward rate constants of 3.4 × 10^?2 m⁶ mol^?2 s^?1 for R-PSA and 9.96 × 10^?3 m⁶ mol^?2 s^?1 for S-PSA. These data will be useful in the design of extraction processes.     

Kinetics and mechanism of oxidation of aurate(I) by peroxydisulphate in aqueous hydrochloric acid

The reaction between Au(I), generated by reaction of thallium(I) with Au(III), and peroxydisulphate was studied in 5 mol dm^?3 hydrochloric acid. The reaction proceeds with the formation of an ion‐pair between peroxydisulphate and chloride ion as the Michealis–Menten plot was linear with intercept. The ion‐pair thus formed oxidizes AuCl₂^? in a slow two‐electron transfer step without any formation of free radicals. The ion‐pair formation constant and the rate constant for the slow step were determined as 113 ± 20 dm^?3 mol^?1 and 5.0 ± 1.0 × 10^?2 dm³ mol^?1 s^?1, respectively. The reaction was retarded by hydrogen ion, and formation of unreactive protonated form of the reductant, HAuCl₂, causes the rate inhibition. From the hydrogen ion dependence of the reaction rate, the protonation constant was calculated to be as 0.6 ± 0.1 dm³ mol^?1. The activation parameters were determined and the values support the proposed mechanism. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 589–594, 2002     

The chemistry and kinetic behavior of Cu-Cr-As/B wood preservatives. I. Fixation of chromium on wood

The kinetic behavior of CrO₃ in its reaction with wood has been elucidated. Various reactions take place between CrO₃ and the lignin and cellulose in wood. CrO₃ reacts with cellulose in a two-step reaction: the first step is an adsorption of Cr^VI onto the cellulose to form Cr^VI/cellulose activated complexes. The second step is a Cr^VI → Cr^III reduction taking place on the cellulose surface. The Cr^III formed is only physically adsorbed to the cellulose or very weakly bound as small amounts of Cr^III can be released into the reaction medium. The Cr^VI adsorbed by cellulose appears mainly to be reduced to Cr^III. The reaction of Cr^VI with lignin has been shown to be the composition of the three successive reaction of Cr₂O₇^2?, HCrO₄^?, and CrO₄^2? with the guaiacyl units of lignin. Insoluble and stable Cr^VI/lignin complexes in which chromium maintains its hexavalent oxidation state are formed. Rate constants and energies of activation for all the reactions have been determined. The fixation of CrO₃-derived compounds on wood has been explained as the combination of the various reactions investigated. The results indicate that 60% of Cr is fixed irreversibly to the lignin of wood as Cr^VI and 40% is weakly bound, probably just precipitated, on the cellulose surface as Cr^III of which small amounts can be released in a water medium. The complex Cr^VI and Cr^III species forming complexes with the guaiacyl units have been identified.     

Picosecond laser studies of the charge-transfer reaction of excited triplet diphenylcarbene with electron donors

Evidence of a one-electron transfer process in a carbene reaction has been observed for the first time. The example is the quenching of the photoexcited triplet state of diphenylcarbene (³*DPC) by electron donors. Measurement of the fluorescence lifetime as a function of donor concentration yielded the bimolecular rate constant, ³*k. An explanation is offered as to why ³* and ¹DPC react efficiently with amines as well as alcohols, whereas the ground triplet, ³DPC, does not.     

Kinetic Study of Hydrogen–Deuterium Exchange of Glutamic Acid in Deuterated Hydrochloric Acid Solution

The kinetics of the hydrogen–deuterium (H–D) exchange at both the methine (alpha) and methylene (gamma) positions of glutamic acid in deuterated hydrochloric acid solution has been studied in the temperature range of 383–433 K by ¹H NMR detection. The reaction rates of H–D exchange at the two positions were described by applying multivariable linear regression (MLR) analysis and are determined as v = k[Glu]^3.3[D₃O⁺]^1.5 mol L^?1 h^?1 with k = 3.52 × 10¹⁶ × exp (–1.37 × 10⁵/RT) mol^?3.8 L h^?1 for the alpha position as well as v = k[Glu]^1.0[D₃O⁺]^0.45 mol L^?1 h^?1 with k = 1.77 × 10¹² × exp (–0.99 × 10⁵/RT) mol^?0.45 L h^?1 for the gamma position. The Arrhenius activation energy (E_a) at the gamma position is less than that at the alpha position, which implies that the deuteration reaction at the gamma position proceeded more easily.