Reactions of 1,2,2,2-tetrachloroethyl isocyanate with trialkyl and trimethylsilyl phosphites

The reaction of 1,2,2,2-tetrachloroethyl isocyanate with trialkyl phosphites is unselective. It involves chlorine substitution, addition by the isocyanate group, and dehydrochlorination and gives rise to a mixture of mono- and diphosphorylated compounds. Diethyl trimethylsilyl phosphite more selectively reacts with 1,2,2,2-tetrachloroethyl isocyanate. At a 1:1 molar reagent ratio, an -phosphorylated trichloroethyl isocyanate is formed, and at a 2 : 1 ratio, chlorine substitution and addition by the isocyanate group take place to give a related 1,3-diphosphonate.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004, pp. 1456–1459.Original Russian Text Copyright © 2004 by Onysko, Maidanovich, Sinitsa.This revised version was published online in April 2005 with a corrected cover date.     

New materials for sorption of hydrogen

The influence of temperature, duration of thermal treatment, and oxidation modes of the aluminum base on processes in which intermetallic compounds LiLaAl are formed by the method of electrochemical cathodic intercalation was studied. The optimal modes of formation of LiLaAl_ox compounds exhibiting high sorption capacity for hydrogen were determined.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 9, 2004, pp. 1516–1519.Original Russian Text Copyright © 2004 by Olshanskaya, Sobgaida, Popova.     

Evaluation of sorption affinity of cadmium(II) on Haro river sand from aqueous solutions

The sorption of Cd(II) on Haro river sand from deionized water is reported. The sorption system obeyed according to the Freundlich and Dubinin–Radushkevich (D-R) isotherms. The Freundlich parameters 1/n = 0.67±0.05 and of A = 1.38±1.14 mmole·g^-1 have been ascertained. D-R isotherm yields the values of = -0.003741±0.000321 kJ²·mole^-2, X _m = 0.23±0.21 mole·g^-1 and of E = 11.6±0.5 kJ·mole^-1. The influence of common anions and cations on the sorption was examined. Trivalent Bi enhances the sorption whereas Fe, Cr, Al and chromate ions reduce the sorption significantly. Hf(IV) and Ag(I) indicate substantial sorption (61–98%) whereas Gd(III), Re(VII) and Sc(III) show low sorption (<5%). The elements having low sorption can be separated from elements indicating higher sorption using Haro river sand column.     

Sorption of radioiodine on organic rich soil,clay minerals and alumina

Batch method was used to investigate the sorption behavior of radioiodine on organic rich soil, alumina, chlorite-illite clay mixture and bentonite.¹³¹I was used as tracer. The grain sizes of the samples used were all below 38 m. A rather slow kinetics was observed for the adsorption of radioiodine on organic rich soil. The distribution ratio increased with increasing solution/solid (V/m) ratio, and the contact time. The pH of the synthetic groundwater did not change the distribution ratio appreciably. The soil biomass however, showed a striking effect on the adsorption of radioiodine. Among the clay minerals, the highest distribution ratio value was found for chlorite-illite clay mixture. All the values were however well below those of the organic rich soil. The sorption data were fitted to Freundlich and Dubinin-Radushkevich types isotherms. Means energies of adsorption, as well as the affinity ratios of the sorption sites to iodine and chlorine were calculated.     

Measurements of Heat of Zeolite Dehydration by Scanning Heating

A procedure for measurement of the heat of zeolite dehydration by scanning heating has been designed. Simultaneous data on heat flow (DSC) and mass loss (TG) are required for evaluation. The heating rate depends on the experimental conditions (point-spread function, sample mass, crucible design, and calorimetric reproducibility). Dehydration measurements have three advantages as compared with the sorption procedure: i) one can investigate samples with irreversible dehydration; ii) no approximation model is needed for calculation of the partial molar heat of dehydration; and iii) the procedure is not labor-consuming.The procedure was tested on the natural zeolites heulandite, chabazite and mordenite. The results are close to those measured by the sorption procedure. The partial molar heat of dehydration was found to depend on the water content. It increases from 50 to 87 J mol^–1 K^–1 for heulandite, from 53 to 81 J mol^–1 K^–1 for chabazite, and from 51 to 71 J mol^–1 K^–1 for mordenite.The approximation of the heat of sorption by linear regression was found to be wrong. Detection of a phase transitioN after this approximation has no meaning.This revised version was published online in November 2005 with corrections to the Cover Date.     

Chlorine loss from polyvinylchloride under neutron irradiation

PVC samples were irradiated for 1 hour with a thermal neutron flux of _th =4.71·10¹¹n·cm^–2·s^–1 and the chlorine lost during irradiation was measured by -ray spectrometry. About 15% of loss of chlorine has been observed for untreated samples while samples heated to temperatures of 60 and 80°C for one minute before irradiation have been found to loose about 8% and 3%, respectively. The results indicate an influence of the polymer structure on the release of chlorine.     

Structure of oxygen clathrate hydrate by neutron powder diffraction

Oxygen hydrate was prepared by reacting oxygen with deuteriated ice at high pressure. Its structure was examined with powder neutron diffraction. It was found to crystallize in the cubic space group witha=17.070(1) Å. The formation of the type II structure rather than type I can be attributed to the larger Langmuir constant of sorption for the oxygen molecules in the 12-hedral cages. The encaged oxygen molecules are orientationally disordered. A comparison of the oxygen thermal parameters in both cages suggests the existence of local potential minima in the 16-hedral cages.Published as NRCC 25940     

Quantum-chemical investigation of the localization and hydration of Ca<Superscript>2+</Superscript> and Mg<Superscript>2+</Superscript> cations in eight- and ten-fold structural rings in the clinoptilolite structure

The hydration of Ca²⁺ and Mg²⁺ exchange cations in solution and in 10- and 8-membered silicon—oxygen rings of the clinoptilolite was studied by ab initio and MNDO quantum-chemical methods. The coordination numbers of these cations with respect to water molecules and their hydration energies were determined. It is shown that the localization of Ca²⁺ and Mg²⁺ in the clinoptilolite structure was different for the dehydrated state and the partially hydrated state. The ion exchange sorption energy calculated for the Ca²⁺—Mg-Cli system was in satisfactory agreement with the experimental data.Translated from Teoreticheskaya i Éksperimentalnaya Khimiya, Vol. 40, No. 6, pp. 357–362, November–December, 2004.     

Application of the denuder technique in filter sampling of airborne chromates at ground level concentrations

The use of the denuder technique for the preserving sampling of chromium(VI) in airborne dust at ground level (immission) concentrations was investigated. A simple denuder with activated charcoal retained by a steelwire-net cylinder was constructed. The sorption abilities of the denuder towards sulfur dioxide, which is responsible for the reduction of sampled Cr(VI) on the filter surface, were examined under various conditions. The measurements provide evidence for a laminar flow inside the denuder. At a flow rate of 100 L/h and a temperature of 27 °C the theoretical sorption value of 99.6% is reached within an experimental error of ±0.1%. A relative humidity of 19–91.5% has no influence on the sorption. In order to check if an experimental sorption value of 99.5% is sufficient to stabilize Cr(VI) on the filter surface, sampling was simulated by sucking SO₂-loaded air through Teflon filters loaded with Cr(VI) containing aerosol particles with diameters of about 0.3 m. Aerosols of two different compositions were generated by a sprayer in combination with a diffusion dryer. The particle size distributions were determined from scanning electron microscopic pictures. Chromium(VI) was eluted from the filters with an alkaline buffer and extracted from the filter eluates with a solution of a liquid anion exchanger. Chromium was determined with graphite furnace atomic absorption spectrometry. The Cr(VI) losses are between 57 and 16% depending on the composition of the aerosol particles and the sampling time. Realistic conditions were chosen regarding the initial Cr(VI) on the filters and the amount of sulfur dioxide which passed through the denuder.Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday     

Simple route to secondary amides of phosphorylacetic acids and their use for extraction and sorption of actinides from nitric acid solutions

An efficient method for the synthesis of secondary alkylamides of phosphorylacetic acids (APA) was proposed. The method involves amidation of ethyl phosphorylacetates with primary aliphatic amines. The scope of reaction was determined. Reactions with ethylenediamine and 1,4-diaminobutane yield the corresponding bisamides; in the case of 1,3-diaminopropane, N-(3-aminopropyl)diphenylphosphorylacetamide or N,N-propylenebis(diphenylphosphorylacetamide) was obtained, depending on the reaction conditions. The extraction of americium(III) complexes and the sorption of uranium(VI) by sorbents with physically sorbed APA from nitric acid solutions were studied. There is no correlation between the partition coefficient of americium(III) and the structure of APA; in the sorption of uranium(VI), the degree of extraction depends on the complexone structure.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2394–2402, November, 2004.     

Characterization of the sorption of uranium(VI) on different complexing resins

The sorption of uranium(VI) on two cationic resins containing different complexing groups, the iminodiacetic resin Chelex 100 and the weak carboxylic resin Amberlite CG-50, was investigated. The Gibbs–Donnan model was used to describe and to predict the sorption through the determination of the intrinsic complexation constants. These quantities, even though non-thermodynamic, characterize the sorption as being independent of experimental conditions.The sorption mechanism of the metal on the complexing resins was also studied by adding a competitive soluble ligand that shifts the sorption curves to higher pH values. The ligand competes with the resin for the complexation with the metal ion. Uranium is also strongly sorbed on Chelex 100 at very acid pH, through formation of two complexes in the resin phase: ML with log_110i=–1.16, in more acidic solution, and ML₂ with log_120i=–5.72. Only the presence of the competitive ligand in solution makes the determination of the second complex possible. Also on Amberlite CG-50 the sorption is strong and involves the formation of the complex ML₂, in more acidic solution, with log_120i=–3.16. In the presence of the ligand EDTA, the complex ML₂(OH)₂ was characterized with log_12–2i=–5.15. In all the experiments the hydrolysis reaction in the aqueous phase was quantitatively considered.     

Chlorine and bromine contents in tobacco and tobacco smoke

The chlorine and bromine contents in tobacco and tobacco smoke in both the particulate and gaseous phases were studied by neutronactivation analysis. Methyl chloride and methyl bromide concentrations were measured in the gaseous phase by gas-liquid chromatography — mass spectrometry. The chlorine and bromine contents in nine brands of cigarettes were on the average as follows: Tobacco—6600 ppm chlorine and 110 ppm bromine. Cigarette smoke, particulate phase—68 g chlorine and 1 g bromine per cigarette. Cigarette smoke, gaseous phase—90 g chlorine and 5 g bromine per cigarette. In the gaseous phase methyl chloride accounted for 60% of the total chlorine and methyl bromine for 80% of the total bromine.     

Sorption of hafnium on hydrous titanium oxide using radiotracer technique

The sorption of hafnium on hydrous titanium oxide (TiO₂·1.94 H₂O) has been studied in detail. Maximum sorption of hafnium can be achieved from a pH 7 buffer solution containing boric acid and sodium hydroxide using 50 mg of the oxide after 30 minutes shaking. The value ofk _d, the rate constant of intraparticle transport for hafnium sorption, from 0.01M hydrochloric and perchloric acid and pH 7 buffer solutions has been found to be 17 mmole·g^–1·min^–2. The kinetics of hafnium sorption follows Lagergren equation in 0.01M HCl solution only. The values of the overall rate constantK=6.33·10^–2 min^–1 and of the rate constant for sorptionk ₁=6.32·10^–2 min^–1 and desorptionk ₂=2.28·10^–5 min^–1 have been evaluated using linear regression analysis. The value of correlation factor() is 0.9824. The influence of hafnium concentration on its sorption has been examined from 4.55·10^–5 to 9.01·10^–4 M from pH 7 buffer solution. The sorption data followed only the Langmuir sorption isotherm. The saturation capacity of 9.52 mmole·g^–1 and of a constant related to sorption energy have been estimated to be 2917 dm³·mole^–1. Among all the additional anions and cations tested only citrate ions reduce the sorption significantly. Under optimal experimental conditions selected for hafnium sorption, As(III), Sn(V), Co(II), Se(IV) and Eu(III) have shown higher sorption whereas Mn(II), Ag(I) and Sc(III) are sorbed to a lesser extent. It can be concluded that a titanium oxide bed can be used for the preconcentration and removal of hafnium and other metal ions showing higher sorption from their very dilute solutions. The oxide can also be employed for the decontamination of radioactive liquid waste and for pollution abatement studies.     

The uptake of strontium by calcium phosphate phase formed at an elevated pH

The sorption of radioactive strontium by poorly crystalline hydroxyapatite (HA) obtained by the transformation of amorphous calcium phosphate (ACP) at initial pH 10.8, was investigated. Morphological analysis, performed by transmission electron microscopy, has demonstrated that the solid phase consists of nanometer size ultra-micro particles connected into spherical aggregates. A maximum sorption capacity, determined as the asymptote of the sorption isotherm was =(3.8±0.3)·10^–2mol Sr/mol P. Based on this result and the structural conditions, a possible theoretical explanation for the incorporation of a strontium ion into the apatite lattice has been proposed.     

Sorption of cobalt on bentonite

Sorption of Co on bentonite has been studied by using a batch technique. Distribution coefficients (K _d ) were determined for the bentonite-cobalt solution system as a function of contact time, pH, sorbent and sorbate concentration and temperature. Sorption data have been interpreted in terms of Freundlich, Langmuir and Dubinin-Radushkevich equations. Thermodynamic parameters for the sorption system have been determined at three different temperatures. The positive value of the heat of sorption, H ⁰=22.08 kJ/mol at 298 K shows that the sorption of cobalt on bentonite is endothermic, where as the negative value of the free energy of sorption, G ⁰=–10.75 kJ/mol at 298 K shows the spontaneity of the process. G ⁰ becomes more negative with an increase in temperature which shows that the sorption process is more favourable at higher temperatures. The mean free energyE7.7 kJ/mol for sorption of cobalt on bentonite shows that ion-exchange is the predominant mode of sorption in the concentration range of the metal studied i.e. 0.01 to 0.3 mol/dm³. The presence of some complementary cations depress the sorption of cobalt on bentonite in the order of K⁺>Ca²⁺>Mg²⁺>Na⁺. Some organic complexing agents and natural ligands also affect the sorption of cobalt. The desorption studies with ground water at low cobalt loadings on bentonite show that about 97% metal is irreversibly sorbed.     

Boron and gadolinium neutron capture therapy

The principles of neutron capture therapy of tumor diseases, the types of drugs, and the results of their clinical applications are discussed.Based on the report presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry dedicated to the 50th anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (Moscow, May 30–June 4, 2004).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1795–1812, September, 2004.     

Thermodynamic and magnetic resonance studies on the hydration of polymers: I. Interactions of water in a synthetic cation-exchange resin

Measurements of NMR spin-lattice relaxation times T ₁ were performed for sorbed H₂O and D₂O in a sulfonated ion-exchange resin at varying degrees of hydration with alkaline cations as counter ions. From the sorption isotherms at three different temperatures the partial molar enthalpies and entropies of sorption show a minimum for all alkaline cations at water concentrations of n 0.8, i.e., there are 0.8 water molecules per –SO ₃ ^– group. The first water molecules sorbed in the ion-exchange resin matrix are characterized by anisotrtopic rotational diffusion processes with correlation times of the order of ₁ 50 ns and ₂ 30 ps, respectively. This indicates that they are located in the electrostatic field between the corresponding ion pair. Although these two correlation times are very similar at a given temperature for all alkaline cations studied in the present investigation, the existence of a second spin-lattice relaxation time for sorbed H₂O at n=0.8 indicates that for Cs about 50% of the sorbed water diffuses between locations in the resin. This fraction decreases with ionic radii and with falling temperatures. For Li the amount is less than 20%.