Experimental determination of covalent radii of elements

The results of direct experimental determination of covalent bond lengths in molecular structures are presented. This made it possible to establish the values of normal covalent radii. The recommended values of covalent radii for 56 elements are tabulated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2349–2354, December, 1995.     

Determination of Ionic Radii from Metal Compressibilities

The critical degrees of metal compression were determined from the experimental equations of state. The degree of metal compression corresponds to the cation-cation contacts in the structure. The cation radii were determined from the metal compressibilities and are in satisfactory agreement with the empirical values.Original Russian Text Copyright © 2004 by S. S. Batsanov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 941–944, September–October, 2004.     

Ein Beitrag zur Stereochemie des Arsens in As(III)—Sauerstoffverbindungen

The oxygen coordination sphere around As(III) consists of the three primary oxygen atoms (average As–O distance 1.78₅ Å) and secondary oxygen atoms between 2.70 and 3.37 Å (3.37 Å is the assumed sum of theVan der Waals radii). Reasons are discussed why neither the number (0–3) nor the length of the secondary As–O distances exert an influence on the geometry of the [AsO₃]-group and its As–O distances.

     

Neodym-Perowskitcarbide und -nitride

Zusammenfassung Perowskit-Carbide werden in den Systemen Nd–{Ga, In, Pb} –C aufgefunden. Ferner existiert ein Perowskit-Nitrid Nd₃AlN und wahrscheinlich auch die analogen Verbindungen in den Dreistoffen: Nd–{Ga, In, Tl, Sn, Pb}–N. Die Abhängigkeit der Gitterparameter von der Größe des dreiwertigenS.E.-Ions sowie der Bindungsmechanismus werden diskutiert.

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Perovskite carbides have been detected within the ternary systems Nd–{Ga, In, Pb}–C. Nd₃AlN is a perovskite nitride; the analogous compounds occur very likely in the systems: Nd–{Ga, In, Tl, Sn, Pb}–N. The dependency of the lattice parameters versus the radii of the trivalentR.E. ions and the bonding mechanism are discussed.

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Mit 4 Abbildungen     

Diels-Alder reaction volumes in the solid state and solution

The densities of anthracene, tetracyanoethylene, maleic anhydride, N-phenylmaleineimide, trans, trans-1,4-diphenylbuta-1,3-diene, and their Diels-Alder adducts were measured in the solid state and in solution at 25 °C. The reaction volumes in the solid state were calculated from the difference in molar volumes. They turned out to be low, close to each other (–4 to –11 cm³ mol^–1), and slightly different from the reaction volumes (–8±1 cm³ mol^–1) calculated from the van der Waals radii. The reaction volumes in solutions (–15 to –32 cm³ mol^–1) were found from the difference in partial molar volumes of the reactants in dioxane, acetonitrile, and 1,2-dichloroethane, The experimental Diels-Alder reaction volumes in solution are determined not only by the formation of new bonds in an adduct: a considerably higher contribution (to 75%) is made by a change in the volume of intermolecular empty spaces in solution on going from reactants to adducts.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2386–2390, November, 2004.     

Anisotropy of the van der Waals Configuration of Atoms in Complex,Condensed, and Gas-Phase Molecules

Anisotropic van der Waals (vdW) radii of 5b–7bsubgroup elements were determined from structures of gas-phase van der Waals complexes and crystal molecular compounds. The anisotropy of the van der Waals configuration of atoms was shown to decrease when going from isolated molecules to the condensed state. Variations in intermolecular distances, which are usually explained in terms of the formation of hydrogen bonds, are substantially governed by the anisotropic effect.     

Dependence of computer model structure of an amorphous solid on hardness of the repulsive potential

In models of an amorphous solid with a potential U = ar_–n(n = 3–20), the main structural elements were found to be tetrahedron and quartoctahedron. At lower n there are more tetrahedra and less quartoctahedra. In addition to the fom and size of separate Delaunay simplices, their mutual arrangement has been studied by percolafion analysis. For that we used the coloring of the Voronoi network: according to tetrahedricity of simplices to identify dense atomic configurations, and according to the radii of mouths of cavities (passages between simplices) to identify the cavities. We have found percolative cavities in liquids and percolating dense configurations in all amorphous solid models.Institute of Chemical Kinetics and Combustion, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 5, pp. 94–105, September–October, 1993.Translated by L. Smolina     

Van der Waals radii of metals from spectroscopic data

The lack of information about the van der Waals radii of metals can be compensated for by using the results of spectroscopic investigations of van der Waals molecules. It has been shown that the interatomic distances in these molecules obey an additive scheme if one allows for the polarization effects. The van der Waals radii of the alkali metals, Ag, Mg, Zn, Cd, Hg, B, Al, In, and Si, have been determined from the interatomic distances in their heteroatomic molecules with atoms of noble gases. Use of the obtained radii for crystal chemistry is discussed.Translated fromIzyestiya Akademil Nauk. Seriya Khimicheskaya, No. 8, pp. 1374–1378, August, 1994.     

Comparison of oil-soluble and water-soluble initiation of styrene polymerization in a three-component microemulsion

The polymerization of styrene in three-component oil-in-water microemulsions made with the cationic surfactant dodecyltrimethylammonium bromide is studied by dilatometry and quasielastic light scattering as a function of type and concentration of initiator. Fast polymerization rates, high conversions, and high molecular weight polymers are achieved with both oil-soluble (AIBN) and water-soluble (potassium persulfate) initiators. The rate of polymerization shows initiation and termination intervals, but no constant-rate interval is observed. Stable monodisperse microlatexes are obtained with both types of initiators. For both AIBN and potassium persulfate, polystyrene molecular weight is proportional to initiator concentration [I]^–0.4 and particle radii decrease as [I]^–0.2. Polymerization initiation occurs in or at the microemulsion droplets, and polymer particles grow by recruiting monomer and surfactant from uninitiated swollen micelles.     

Van der Waals Gaps in Sm1+x Ba2−x Cu3O y and Their Effect on Superconductivity

We have used electron–positron annihilation to study superconducting cuprates Sm_1+x Ba_2–x Cu₃O _y . We have determined the average radii for oxygen ions in Sm_1+x Ba_2–x Cu₃O _y . Taking into account the ion coordinates and their radii, we have constructed a geometric model for the arrangement of copper and oxygen ions in CuO₂ layers in the [b, c] plane, responsible for the superconductivity. From these data, we have determined the length of the ionic/covalent bonds and the width of the interionic gaps. We have established the effect of the features of the atomic structure of Sm_1+x Ba_2–x Cu₃O _y on the superconducting transition temperature T _c and we have shown that T _c increases as X inceases.     

Approximate sizes of monoatomic negative ions with fractional nuclear charge using electrostatic potentials

Summary Using the criterion that for negative monoatomic ions withN electrons, the location of minimum in the electrostatic potentialV(r) gives an approximate estimate of ionic radii,r _m. Calculations of the latter are reported for quark atoms with fractional nuclear chargesZ=N– andN– , respectively. Quark atoms withN=1–10, 18 and 36 have also been considered.     

Van der Waals radii of elements from the data of structural inorganic chemistry

Van der Waals radii of elements were determined from the data of the structural inorganic chemistry: from intersitial distances in CdX₂- and graphite-type structures, bond lengths in van der Waals molecules, molar volumes of A₂-type substances, refractometry data, and from quantum chemical and correlation ratios. The recommended values of van der Waals radii of elements are tabulated.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 24–29, January, 1995.The author is grateful to the administration of the Department of Chemistry at the University of Durham (Great Britain) for the opportunity to perform this work and to Prof. J. Howard and Prof. K. Wade for useful discussions.     

Thermodynamic evaluation of the zero-valence radii of transition metals

The Mulliken method was used to evaluate the energies of bonds of zerovalent transition metal atoms with ligands, and the strengths of these bonds were found relative to the normal covalent bonds of the same elements. The corresponding atomic radii were calculated and found to be in good accord with experiment.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2347–2348, October, 1989.     

Stability of non-aqueous dispersions

Summary Theoretical values of the magnitude and location of potential energy maxima, of stability ratio and of half-life for colloidal dispersions in hydrocarbon media have been computed from the DLVO theory of colloid stability for spherical particles of radii 200–10,000 Å, and for a range of surface potential (5–80 mV) andHamaker constant (5×10^–13–1×10^–11 erg). The stability relationships show a marked dependence on particle size but are relatively insensitive to the value of theHamaker constant. The results may with some confidence be used to predict the stability of a dispersion in a hydrocarbon medium.

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Zusammenfassung Die Maxima der potentiellen Energie, die Stabilitätsverhältnisse und die Halbwertszeiten von kolloiden Dispersionen in Kohlenwasserstoffen wurden nach der Theorie vonDerjaguin, Landau, Verwey undOverbeek für kugelige Teilchen mit Radien von 200 bis 10000 Å und für Oberflächenpotentiale von 5 bis 80 mV berechnet. Für dieHamaker-Konstante wurden Werte von 5×10^–13 bis 1×10^–11 eingesetzt. Die Stabilität zeigt eine deutliche Abhängigkeit von der Partikelgröße, wird aber von der Größe derHamaker-Konstanten nur wenig beeinflußt.Die Resultate können zu Voraussagen über die Stabilität von Dispersionen in Kohlenwasserstoffen herangezogen werden.

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With 5 figures     

Crystal chemical estimation of polymorphic transformation pressures of covalent compounds

A procedure for the calculation of molar volumes of solids in their polymorphic transformations with increased coordination number is described. Assuming that these transformations occur under high pressures we have calculated the pressures responsible for volume changes using the Murnaghan equation. The same values were estimated based on the principle of equalized intermolecular distances in polymorphic transformations, in satisfactory agreement with the first method. To realize the second procedure, we have obtained volume values of van der Waals radii for the elements of Subgroups 5 to 7b of the Periodic Table.Center of Dynamic High Pressures. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 4, pp. 112–116, July–August, 1993.Translated by T. Yudanova     

Stereospecificity of quenching of excited aromatic molecules by electron acceptors

On the example of fluorescence quenching of perylene by organic electron acceptors we have shown that the radius of the quenching sphere depends on the electron affinity of the oxidizing agent. The deactivation of excited molecules of m-dinitrobenzene was achieved by tunnel electron transfer at a distance, which was significantly greater than the sum of the radii of the reagent molecules. The fluorescence quenching with phthalic anhydride, a weaker electron acceptor, occurs on contact between molecules. The kinetics of this process are described by the Smoluchowski theory of diffusion-controlled reactions. The rate of fluorescence quenching with carbon tetrachloride and nitromethane in polar solvents also increases with the increase of the coefficients of mutual diffusion, but the formal reaction radii of these processes are smaller than the sum of the radii of the interacting particles, which is due to the stereospecifity of the reaction. It was shown that the degree of stereospecificity increases with the decrease of the reaction radius.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 5, pp. 585–590, September–October, 1986.     

Study of the structure of molecular complexes

A cluster of 200 molecules of water containing one of the LiF, LiCl, NaF, NaCl, KF or KCl ion pairs has been studied at the temperature T= 298°K using Monte Carlo techniques. The anion-cation internuclear separations considered in this work for any of the above pairs are 6.0 Å, 8.0 Å and 10.0 Å. The water-water potential is obtained from quantum-mechanical Hartree-Fock type computations corrected by inclusion of dispersion forces; the ion-water potentials have been obtained from Hartree-Fock type computations on the single ion-water complex. The computed radii for the first hydration shell are 2.7±0.1 Å, 3.4±0.3 Å, 4.0±0.3 Å, 3.0±0.5 Å, and 3.9±0.4 Å, for Li⁺, Na⁺, K⁺, F^– and Cl^–, respectively. The computed coordination numbers are 5.4±0.7,6.0±1.1, 7.2±1.2,4.5±0.6 and 5.1±0.8 for the same ions, respectively. The range of the coordination number obtained from compressibility, enthalpy, NMR spectroscopy and other experimental methods is much larger than the error ranges above given. Therefore the Monte Carlo simulation provides reliable information on the cluster shape, cluster structure and on the coordination numbers and hydration shell radii for the cations and anions, when both are present in a water cluster.     

Electronic structure,energy of hydration,and stability of metal aquo ions

The stability of metal aquo ions with respect to redox reactions is determined by the ionization energies of the atoms and the Gibbs energies of hydration for the ions(–_hG⁰). We present critically selected values of –_hG⁰ for 55 metal ions, determined from electrochemical, thermochemical, and spectra data. We consider the factors determining the values of –_hG⁰ (charges, ionic radii, electronic structure, and relativistic effects). For isoelectronic ions, we observe correlations between the ratios of the Gibbs energies of hydration for these ions with different charges and the ratios of their ionic radii. Based on the use of these correlations, we find –_hG⁰ for a number of aquo ions not observed experimentally and we estimate the unknown oxidation-reduction potentials for the pairs of ions M³⁺/M²⁺. We formulate the principles for stabilization of unstable oxidation states of the metals by including the corresponding ions in complexes with certain classes of ligands.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 30, No. 1, pp. 1–11, January–February, 1994.     

Adsorption of Strontium on Illite

Adsorption of strontium on illite type clay has been studied as a function of shaking time, the ratio of solution volume to weight of clay and the concentration of adsorbate, using ⁹⁰Sr as a tracer. The adsorption experiments were carried out using the batch method and initial Sr²⁺ ion concentrations ranged from 10^–6 to 10^–1 M. The influence of Ca²⁺ and Ba²⁺ cations on Sr adsorption were also studied. These effects are correlated with the ionic radii of alkaline earth ions present in the solution. The Freundlich and Dubinin Radushkevich (D-R) isotherm have been applied to the data and the parameters of the isotherm equations were calculated. The mean energy of adsorption, E was also calculated from the adsorption energy constant, K and maximum capacity X _m values were determined from linearized D-R equation. From empirical Freundlich parameters a site distribution function was calculated.     

Surface characterization and heats of adsorption of chromatographic alumina gel

The porous nature of chromatographic alumina gel has been investigated by adsorption/condensation processes and electron microscopy. Having 63% porosity, the gel is very porous. Total pore volume as determined by the fluid-displacement method is 0.497 cm³ g^–1. Its specific surface area, as determined by water vapor adsorption, is 225 m² g^–1. Micropore volume, as determined by utilizing Gurwitsch's rule, turns out to be 0.262 cm³ g^–1. The greater portion of the surface area and pore volume occurs in small and transitional pores, with average pore radii (hydraulic) less than 2.1 nm.Organic vapors, such as methyl ethyl ketone, acetone, methyl acetate, and methyl alcohol, were adsorbed on the gel between 0 and 36°C under vacuum, and the data were recorded on a Cahn-1000 electrobalance device. Isosteric heats of adsorption were calculated by applying the Clausius Clapeyron equation to the adsorption isosters at different surface coverages. Two types of adsorption processes, one with low activation energy and other with high activation energy can be distinguished. The increase in values ofq _st indicates that increasing temperature changes physical adsorption into chemisorption.