Reactions and phases within the TeO2-rich part of the Bi2O3-TeO2 system

The complexes of heavy lanthanides and yttrium with 2,3-dimethoxybenzoic acid of the formula: Ln(C₉h₉O₄)₃·nH₂O, where Ln=Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), Lu(III), Y(III), and n=2 for Tb(III), Dy(III), Ho(III), Y(III), n=1 for Er(III), Tm(III), n=0 for Yb(III) and Lu(III) have been synthesized and characterized by elemental analysis, ir spectroscopy, thermogravimetric studies and x-ray diffraction measurements. The complexes have colours typical for Lnł³⁺ ions (Tb(III), Dy(III), Tm(III), Yb(III), Lu(III), Y(III) - white; Ho(III) - cream and Er(III) - salmon). the carboxylate groups in these complexes are a symmetrical, bidentate, chelating ligand or tridentate chelating-bridging. they are isostructural crystalline compounds characterized by low symmetry. On heating in air to 1273 k the 2,3-dimethoxybenzoates of heavy lanthanides and yttrium decompose in various ways. The complexes of Tb(III), Dy(III), Ho(III), Er(III), Tm(III) and Y(III) at first dehydrate to form anhydrous salts which next are decomposed to the oxides of the respective metals. 2,3-dimethoxybenzoates of Yb(III) and Lu(III) are directly decomposed to oxides. When heated in nitrogen the hydrates also dehydrate in one step to form the anhydrous complexes that next form the mixture of carbon and oxides of respective metals or their carbonates. The solubility of the yttrium and heavy lanthanide 2,3-dimethoxybenzoates in water at 293 k is of the order of 10^-2 mol dm^-3. This revised version was published online in July 2006 with corrections to the Cover Date.     

Critical point,singularities and extrapolations in the helium iso-electronic sequence

The Z-expansion of two-electron systems is analyzed with the Padé technique with emphasis on establishing analytical properties of the function E(Z) formally associated with the power series expansion. The concept of critical point in this connection is stressed. For this sequence it occurs at Z_c = 0.911246 with E(Z_c) = ?0.415184. The structure of E(Z) for Z < Z_c is investigated. The use of Padé approximants to extrapolate values of electron affinities is emphasized.     

Critical point estimation of the Lennard-Jones pure fluid and binary mixtures

The apparent critical point of the pure fluid and binary mixtures interacting with the Lennard-Jones potential has been calculated using Monte Carlo histogram reweighting techniques combined with either a fourth order cumulant calculation (Binder parameter) or a mixed-field study. By extrapolating these finite system size results through a finite size scaling analysis we estimate the infinite system size critical point. Excellent agreement is found between all methodologies as well as previous works, both for the pure fluid and the binary mixture studied. The combination of the proposed cumulant method with the use of finite size scaling is found to present advantages with respect to the mixed-field analysis since no matching to the Ising universal distribution is required while maintaining the same statistical efficiency. In addition, the accurate estimation of the finite critical point becomes straightforward while the scaling of density and composition is also possible and allows for the estimation of the line of critical points for a Lennard-Jones mixture.     

Theoretical and experimental study of lone pair interactions in THF/chloranilic acid system

Crystallization of a multi-component molecular crystal that consists of chloranilic acid with THF as solvate afforded the general formula C₆H₂O₄Cl₂·THF. Its crystal structure is new and reveals new example of cooperative lone pair–π interactions (oxygen of THF to centroid of chloranilic distance of 3.258 Å) beside others (e.g., hydrogen bonding OH···O) with new experimental evidence of receptor/solvent as a lone pair donor. This has been supported by computational methods, mainly, DFT and RIMP2 levels of theory (?48.3 kJ/mol). In addition, several potential curve surfaces are obtained to test the strength and type of every notable interaction in the lattice.     

Critical point measurement of some polycyclic aromatic hydrocarbons

The critical temperatures and the critical pressures of five polycyclic aromatic compounds, namely, acenaphthene, fluorene, anthracene, phenanthrene, and pyrene have been measured. All the compounds studied decompose at near-critical temperatures. A pulse-heating technique applicable to measuring the critical properties of thermally unstable compounds has been used. The times from the beginning of a heating pulse to the moment of reaching the critical temperature were from (0.06 to 0.85) ms. The short residence times provide little degradation of the substances in the course of the experiments. The experimental critical parameters of the polycyclic aromatic compounds have been compared with those estimated by five predictive methods. The acentric factors of polycyclic aromatic compounds studied have been calculated.     

On the competition between scavenging and recombination in solutions of macromolecules

This paper is concerned with the competition between recombination of a radical pair and radical attack on targets such as macromolecules or nanoparticles in solution, which are large on the molecular scale. The difference in scale between radicals and targets causes the kinetics to be transient over a long period. The specific novel feature of the analysis is the effect of the initial spatial correlation of the radicals on the kinetics of attack on the targets. The main results are (i) a simple modification of the Smoluchowski rate coefficient for scavenging and (ii) the probability of multiple hits on the same target. Both effects arise from the clustering of the radicals. The latter is of particular interest in radiation biology, because multiple hits result in complex damage. The analysis is validated against results from random flights computer simulation; excellent agreement is obtained.     

Calculation of the long-range coupling between electrons in lone pairs and double bonds using semiempirical and ab initio methods

The electronic coupling between symmetrically placed lone pairs or π electrons are calculated using semiempirical and ab initio methods and the results compared to experimental numbers. The agreement is satisfactory in cases when there is a small tendency for cancellation between contributions of different signs. We have found nonexponential behavior when the number of intervening cyclohexane units is increased in the case of phenyl endgroups. In this case as well as in the cases with exponential decrease, the CNDO /S method shows a similar behavior as that of the ab initio Hartree–Fock method, which suggests that the former method may be used to calculate the electronic factor in electron transfer systems. © 1992 John Wiley & Sons, Inc.     

The relationship between the inflection point and equivalence point of a potentiometric titration

Attention is drawn to a common textbook error concerning the coincidence of the end-point and equivalence point of potentiometric titration curves.     

On the competition between linear and cyclic isomers in second-row dicarbides

Second-row dicarbides C(2)X (X = Na-Cl) are investigated with quantum mechanical techniques. The cyclic-linear competition in these systems is studied, and the bonding scheme for these compounds is discussed in terms of the topological analysis of the electronic density. C(2)Na, C(2)Mg, C(2)Al, and C(2)Si are found to prefer a C(2)(v)-symmetric arrangement corresponding to a T-shape structure. On the other hand, for C(2)P, C(2)S, and C(2)Cl the linear isomer is predicted to be the ground state. A detailed analysis of the variation of the electronic energy and orbital energies with the geometry has been carried out. A simple theoretical model, taking into account the main interactions between the valence orbitals of both fragments, the X atom and the C(2) molecule, allows an interpretation of the main features of these compounds.     

Hexaferrites and phase relations in the iron-rich part of the system Sr-La-Co-Fe-O

The iron rich part of the system was examined in the temperature range of 1200-1380 °C in air, with focus on the solid solutions of M-type hexaferrites. Samples of suitable compositions were studied by electronprobe microanalysis (EPMA). Substituted Sr-hexaferrites in the system Sr-La-Co-Fe-O do not follow the 1:1 substitution mechanism of La/Co in M-type ferrites. Due to the presence and limited Co²⁺-incorporation Fe³⁺-ions are reduced to Fe²⁺ within the crystal lattice to obtain charge balance. In all examined M-type ferrites divalent iron is formed, even at 1200 °C. The substitution principle Sr²⁺+Fe³⁺↔La³⁺+(Fe²⁺, Co²⁺) yields to the general substitution formula for the M-type hexaferrite Sr²⁺_1-xLa³⁺_xFe²⁺_x-yCo²⁺_yFe³⁺_12-xO¹⁹ (0≤x≤1 and 0≤y≤x). In addition Sr/La-perovskite_SS (_SS=solid solution), Co/Fe-spinel_SS, hematite and magnetite are formed. Sr-hexaferrite exhibits at 1200 °C a limited solid solution with small amounts of Fe²⁺ (SrFe₁₂O₁₉↔Sr_0.3La_0.7Co_0.5Fe²⁺_0.2Fe_11.3O₁₉). At 1300 and 1380 °C a continuous solid solution series of the M-type hexaferrite is stable. SrFe₁₂O₁₉ and LaCo_0.4Fe²⁺_0.6Fe₁₁O₁₉ are the end members at 1300 °C. The maximum Fe²⁺O content is about 13 mol% in the M-type ferrite at 1380 °C (LaCo_0.1Fe²⁺_0.9Fe₁₁O₁₉).     

Critical point and vapor pressure of ionic fluids including NaCl and KCl

The critical properties and the vapor and liquid densities of NaCl, KCl, and the primite-model ionic fluid are compared on a corresponding-states basis. In preparation for these comparisons the vapor density of NaCl at very high temperature is calculated from the accurate molecular parameters. The very recent treatment of Gillan is adopted for the primitive model. The liquid properties of KCl and NaCl follow corresponding states exactly but there is some discrepancy for the ion pair in the vapor. The differences are greater for the primitive model but again the agreement is quite good for the liquid. Critical properties are reported for all three fluids.     

Assignment of the four lowest ionized states of p-benzoquinone and the question of “lone pair splitting” in this system

The lowest ionized states of p-benzoquinone are assigned to be n_/²B_3g, n₄/²B_2u, π₁/²B_3u, and π₂/²B_1g in order of increasing energy. This sequence of states confirms Turner's original assignment and invalidates subsequent proposals. The origin of the difficulties with these assignments are traced back to the non-validity of Koopmans' theorem for the “oxygen lone pair” ionizations (i.e., ionization to the n_/²B_3g and n₊/²B_2u states).     

Diffusion in a ternary system and the critical mixing point

Diffusion coefficients were measured for the ternary system water-chloroformacetic acetic acid at 25°C and at five concentrations approaching the critical mixing point. The relationship D₁₁D₂₂–D₁₂D₂₁=0 holding at the critical mixing point has been proven experimentally. By choosing water as solvent instead of acetic acid, negative main diffusion coefficients were found for chloroform, showing an interesting case of incongruent diffusion.     

Relation between the critical point and the precipitation threshold

The relationship between the critical point and the precipitation threshold is examined in the Flory—Huggins approximation with concentration-independent interaction parameter χ. Approximate explicit expressions for the difference between the critical point and the threshold can be derived by series expansion of threshold conditions. In the first-order approximation, the concentration difference depends only on the chainlength averages x_w, x_z, and x_z+1, in the second-order approximation it depends on x_w, x_z, x_z+1, and x_z+2, etc. For polymers of low polydispersity, the second-order approximation gives a good estimate of the concentration difference; for instance, for polymers with exponential distribution and x_w/x_n < 1.25, the error is lower than ca. 1%. The approximation is not suitable for polymers with x_z+1 ? x_z (including polymers whose cloud-point curve exhibits a triple point). Irrespective of the polydispersity of the polymer, the threshold as well as the whole cloud-point curve depend only on the weight-average and higher averages, x_w, x_z, x_z+1, …, x_z+k, where k → ∞; they are, however, independent of the number average x_n.     

Critical point representations of electron density maps for the comparison of benzodiazepine-type ligands

A procedure for the comparison of three-dimensional electron density distributions is proposed for similarity searches between pharmacological ligands at various levels of crystallographic resolution. First, a graph representation of molecular electron density distributions is generated using a critical point analysis approach. Pairwise as well as multiple comparisons between the obtained graphs of critical points are then carried out using a Monte Carlo/simulated annealing technique, and results are compared with genetic algorithm solutions.     

Comparative thermodynamic analysis of the binary system Bi−Sb

Results of the comparative thermodynamic analysis of the binary system Bi?Sb obtained by DTA measurements and predicting are presented in this paper. Activities, activity coefficients, partial and integral molar quantities for Bi and Sb at temperatures 973, 1073 and 1173 K in the investigated binary system Bi?Sb determined by DTA measurements and thermodynamic predicting are given. An excellent agreement between the experimental and predicted results is reached. Also, a phase diagram of the investigated system Bi?Sb obtained by DTA shows good agreement with literature and it can be concluded that DTA could be satisfactorily used for quantitative thermodynamic analysis of any binary system containing equilibrium between solid and liquid solutions. It was also determined that conclusion about linear dependence ofgKs constant for binary eutectic systems and systems with phase transformation is valid for binary system containing equilibrium between solid and liquid solutions too.     

Evaluation of a tube equipped with different inserts: competition between improvements in heat transfer versus increase in pressure drop

Journal of Thermal Analysis and Calorimetry - This study evaluated the efficacy of different inserts incorporation into the simple tube on the rate of improvement in heat transfer as well as the...     

Diffusion competition between solvent and nonsolvent during the coagulation process of cellulose / ammonia / ammonium thiocynate fiber spinning system

An investigation of the diffusion competition between solvent and nonsolvent in a coagulation bath is presented for the formation of a new cellulosic fiber by wet-spinning. The system consisted of the spinnable cellulose solution with a mixture of liquid ammonia/ammonia thiocynate as the solvent and low-molecular-weight alcohols as the nonsolvents. The diffusion competition between solvent and nonsolvent was quantitatively characterized in terms of their mass transfer rate differences. The measurements of this rate difference were performed on the model filament shaped from gelled cellulose solutions. Results revealed that an increase in molecular size of coagulant, bath temperature, and coagulant concentration in the bath enhanced preferential diffusion of solvent from cellulose solution. Fiber spinning experiments showed that a higher value of the initial modulus of the fiber was attained with a coagulation condition providing a lower value of mass transfer rate difference. The importance of mass transfer rate difference was also shown in the influence of the fiber cross-sectional shapes.     

Phase formation and thermal stability of the compounds in the Bi2O3-PbO system

The scientific interest for the Bi₂O₃-PbO system has increased due to the importance of the PbO in the high-T _c superconducting phase formation in the Bi₂O₃-SrO-CaO-CuO system. Also Bi₂O₃-PbO system contains compounds with some specific semiconductor and dielectric properties and Bi₂O₃-based solid solutions are well known as high oxygen ion conductors.Previously, several low melting defined compounds have been identified in the system: 6Bi₂O₃·PbO; 3Bi₂O₃·2PbO; 4Bi₂O₃·5PbO; 4Bi₂O₃·6PbO and Bi₂O₃·3PbO.This work deals with the phase formation and thermal stability of these compounds. Under non-isothermal conditions, in all mixtures regardless of the Bi₂O₃/PbO ratio, the compound 6Bi₂O₃·PbO is preferentially formed, followed by the compound 4Bi₂O₃·5PbO. The formation of the compound 4Bi₂O₃·6PbO was not confirmed while the formation of the compound Bi₂O₃ 3PbO occurs through a complex mechanism which includes an intermediate step in which a solid solution with the litharge structure was identified. Under isothermal conditions in the same temperature range the tendency to form the stoichiometric compounds increases. All compounds form, decompose and melt at temperatures between 530–780°C.     

Keen competition between electrostatic and argentophilic interactions in the formation and behavior of molecular rings

The macrocyclic structures and behavior on the reaction of AgX (X = NO₃ and CF₃SO₃) with bis(nicotinoyl)-4,4′-(9-fluorenylidene)diphenolates (L) have been carried out. Discrete oblong rings and linked rings were constructed via the keen competition between the inter-ring argentophilic (Ag···Ag) interaction and the electrostatic interaction between Ag(I) and its anion, and the interconversion of the two species was attempted by means of anion exchange.