Dissociation constants of phosphoric acid at 25°C and the ion pairing of sodium with orthophosphate ligands at 25°C

The first and second acidity constants of phosphoric acid were determined in a 0.70 ionic strength solution of both a sodium and a potassium ion background salt at 25°C. These experimentally determined constants were compared to literature values as well as values calculated from a theoretical model. Assuming negligible ion pairing of the phosphate ligand with the potassium ions, the stability constants of the NaHPO ₄ ^- and NaH₂PO ₄ ⁰ complexes were determined to be 1.3±0.3 and 0.49±0.07 (mol-L^–1), respectively. These constants were used to model the speciation of orthophosphate in a background of a sodium salt from pH 3 to 10.     

Spectrophotometric Study on the Extraction of 4-(2- Thiazolylazo)Resorcinol Chelates of Cobalt(II), Nickel(II), Copper(II), and Zinc(II) with Zephiramin

Abstract

The solvent extraction of the transition metals(II)4-(2-thia-zolylazo)resorcinol(TAR) chelate anions with cation of zephiramin (Z⁺ Cl^?) was spectrophotometrically investigated. The composition of the extracted species was estimated to be 2Z⁺ MR₂ ^2-, which had the absorption maxima in the same ranges of wavelength at about 550 nm, and the constant extractions were obtained at pH 6.7–10.2 for cobalt, 7.2–9.1 for nickel, 8.2–10.1 for zinc, and 8.5–10.7 for copper system. In the presence of sodium chloride, cobalt chelate could be effectively separated from the other transition metals. The extraction equilibrium was also investigated and the extraction constants were calculated.     

Theoretical investigation of the viscosity of some liquid metals and alloys

The viscosities of some liquid metals and liquid binary alloys have been determined using the theoretical model developed by Morioka et al. (Z. Metallkd. 93, 4 (2002)). The model was applied successfully to the liquid mono-component metals Hg and Na and to the liquid binary alloys Hg–Na, Ag–Cu, Bi–Sn and Ag–Sb. The model successfully described the temperature dependence of viscosity for Hg and Na for a wide range of temperatures. The values of the adjustable parameters k and z were obtained for Hg and Na. For the liquid binary alloys, calculations were done at a particular temperature for each alloy and our results show that for Hg–Na and Ag–Cu there are both qualitative and quantitative agreements between calculated and experimental viscosity data. However, Bi–Sn and Ag–Sb manifested significant levels of quantitative discrepancies between calculated and experimental viscosity data.     

烷基自由基β位裂解反应类反应势垒与速率常数的精确计算

提出反应类等键方法并用于高温燃烧机理中一类重要反应——烷基自由基β位裂解反应的反应势垒和速率常数的精确校正计算. 通过10种不同从头算水平对类反应中5个代表反应的反应势垒的计算发现, 用反应类等键反应方法和直接从头算方法获得的5 个代表反应的反应势垒最大绝对偏差的平均值分别为5.32 和16.16 kJ·mol^-1, 表明反应类等键反应方法计算的反应势垒对不同水平从头算方法的依赖性小, 可在较低从头算水平计算得到精确的反应势垒, 解决大分子体系反应势垒的精确计算问题. 此外应用反应类等键反应方法在BHandHLYP/cc-pVDZ 从头算水平计算了3 个代表反应的速率常数, 并与文献报道的实验值进行了比较, 其在500-2000 K温度区间内计算速率常数与实验速率常数中较大值与较小值的比值k_max/k_min的平均值为1.67, 最大值也仅有2.49. 表明应用反应类等键反应方法在较低从头算水平即可对同类反应的速率常数进行精确计算.最后在BHandHLYP/cc-pVDZ从头算水平用反应类等键反应方法计算了13个烷基自由基β位裂解反应的速率常数.     

Calculation of the equilibrium constants and cooperative parameters of formation of Cu(II) chloride complexes in nonaqueous solvents

Copper(II) distributions over chloride complexes in various organic solvents were analyzed in terms of a modified matrix model. The equilibrium coordination constants of a first ligand and the corrections for the mutual influence between the ligands during the complexation were calculated. It was demonstrated that displacement of the solvent molecule by a chloride ion from the inner coordination sphere of the Cu(II) ion is always of anticooperative character. In MeCN, addition of a chloride ion to a copper ion follows the simplest additive scheme of coordination of the ligand with equivalent coordination vacancies. Possible reasons for nonadditive complexation in DMF, DMSO, trimethyl phosphate, and propylene carbonate are discussed.     

Critical Properties of n-Alkanes and the Relevance of Polymer Models to the Heavy Fluid Metals Rb and Cs

Abstract

n-alkane critical constants as determined experimentally for n ≤ 18 are first compared and contrasted with the predictions of various models. Qualitative accord is found, but only one quantitative prediction, that of Wertheim's model for the critical temperature T_c, is found to fit the experimental data over the admittedly limited range of n available.

Reference is then made to critical properties of the heavy fluid alkali metals, and especially Rb and Cs, where some evidence is cited for the existence of long chains of alkali atoms. The relative constancy of the product of the critical pressure P_c and the critical volume V_c for the three heaviest alkalis is noted, a fact consistent with one of the more recent ‘polymer’ models.     

Kinetics of oxidation of hydroquinone to <Emphasis Type="Italic">p</Emphasis>-benzoquinone catalyzed by microporous metal-organic frameworks M<Subscript>3</Subscript>(BTC)<Subscript>2</Subscript> [M = copper(II), cobalt(II), or nickel(II); BTC = benzene-1,3,5-tricarboxylate] using molecular oxygen

The kinetics of oxidation of hydroquinone (H₂Q) to p-benzoquinone (Q) catalyzed by microporous metal-organic frameworks (MOFs) using molecular oxygen has been investigated. MOF catalysts with different metals and pore sizes, i.e. M₃(BTC)₂(H₂O) _x (M = Cu^II (1), Co^II (2), or Ni^II (3); BTC = benzene-1,3,5-tricarboxylate; x = 3 for MOF 1 and 12 for 2 and 3), were used to catalyze the oxidation reaction. The apparent first-order reaction rate constant increased with increasing temperature, molar ratio of catalyst/H₂Q, and pH of the medium. A kinetic model for the heterogeneous catalysis is proposed, and the apparent activation energy (E _a), the association constants between the hydroquinone and the catalyst (K _s), and the first-order rate constants for product formation in the MOF channels (k _N) were calculated.     

Spectroscopic studies on a ‘turn-on’ fluorescent sensor for transition metals with selective ‘turn-off’ for mercury(II) ions

Spectroscopic studies on a dansyl-based fluorescent sensor N-(4-aminophenyl)-5-(dimethylamino)naphthalene-1-sulphonamide (1) and its interactions with transition metals are reported. The sensor's absorption and emission spectra exhibited different profiles at different polarities and pH values. Enhanced fluorescence was observed in the presence of chromium(III) ions in methanol, while the emission was quenched significantly in the presence of mercury(II) ions both in methanol and aqueous solution. The binding constants of 1 to chromium(III) in methanol and to mercury(II) ions in methanol and aqueous solution were calculated.     

A comparative study of the electrochemical properties of vitamin B-6 related compounds at physiological pH

A comparative study of vitamin B6 group and related compounds in buffered solutions using electrochemical techniques has been performed at neutral pH. Irreversible bi- or tetra-electronic processes are observed for these substances, and the electron transfer coefficient (αn) calculated. It was concluded that either the first or second election transfer were the rate determining step of the electrode process. The diffusion coefficient of these substances was calculated and the values given follow an inverse tendency to the molecular size. For aldehydes the values obtained were corrected of the hydration reaction. It is important to remark that catalytic waves were reported for the first time for these compounds. Using a model involving the nitrogen of the basic structure the kinetic constants were calculated for most of them.     

Kinetics and mechanism of the reaction of hydroxopentaaquarhodium(III) ion with <Emphasis Type="SmallCaps">l</Emphasis>-Arginine in aqueous solution

The kinetics of the aqua ligand substitution from hydroxopentaaquarhodium(III) ion, [Rh(H₂O)₅(OH)]²⁺, by l-Arginine has been studied spectrophotometrically as a function of Arginine concentration, and temperature, at pH 4.3. The reaction proceeds via a rapid outer sphere association complex formation step followed by two consecutive steps. The first of these involves ligand-assisted anation, while the second involves chelation as the second aqua ligand is displaced. The association equilibrium constant for the outer sphere complex formation has been evaluated together with the rate constants for the two subsequent steps. The activation parameters for both steps have been evaluated using Eyring’s equation. Thermodynamic parameters calculated from the temperature dependence of the outer sphere association equilibrium constants are also consistent with an associative mode of activation. The product of the reaction has been characterized by conductivity measurement and IR spectroscopic analysis.     

Correlation of HPLC Retention Data of Triazines with the Inhibition of DHFR from L1210 Cells: Development of New Chromatographic Adsorption Parameter in QSAR

Abstract

The use of chromatographic retention measurements for quantitative structure—activity relationships (QSAR) was investigated by the development of an adjusted logarithmic retention factor. Retention data of 15 triazine derivatives, which inhibit dihydrofolate reductase were measured by HPLC on octyl-silica and silica gel columns. From these data two parameters were calculated. First, the intercept of the plot of the logarithmic retention factor versus acetonitrile concentration was calculated from the reversed-phase retention measurements (log k'o) and, second, the difference between the logarithmic retention factor at high ammonium salt concentration and low ammonium salt concentration in the mobile phase was calculated from retention measurements on the silica gel column. The first parameter represents hydrophobic properties and the second parameter characterizes adsorption properties of the triazine derivatives. The results show a correlation between the two above mentioned parameters and the inhibition of L1210/71 cell growth.     

Kinetic study on the alkaline hydrolysis of 1-aryl-2-phenyl-2-imidazolines. Basicity-rate of hydrolysis and structure relationships

Rate constants (k_obs) of hydrolysis in boiling alkaline ethanolic solution for six 1-aryl-2-phenyl-2-imidazolines were determined. The influence of substituents in the phenyl group at N-1 upon rate of hydrolysis was studied. When the imidazoline ring is considered to be a substituent of the benzene ring at N-1, a good correlation with the Hammett equation is found. It was observed that reaction rates were enhanced by electron-releasing phenyl substituents of N-1 and reduced by electron-withdrawing groups, providing a change in the mechanism of the reaction in the first case that was not observed in the second. Agreement with the Hammett equation allowed comparison between experimental and “calculated” rate constants which are nearly equal. An equation relating the rate constants with the ionization constants of imidazolinium ions is given.     

An approach to the interpretation of backpropagation neural network models in QSAR studies

An approach to the interpretation of backpropagation neural network models for quantitative structure-activity and structure-property relationships (QSAR/QSPR) studies is proposed. The method is based on analyzing the first and second moments of distribution of the values of the first and the second partial derivatives of neural network outputs with respect to inputs calculated at data points. The use of such statistics makes it possible not only to obtain actually the same characteristics as for the case of traditional "interpretable" statistical methods, such as the linear regression analysis, but also to reveal important additional information regarding the non-linear character of QSAR/QSPR relationships. The approach is illustrated by an example of interpreting a backpropagation neural network model for predicting position of the long-wave absorption band of cyane dyes.     

Determination of Kinetic Parameters from GPC-Data

Abstract

The molecular weight distribution and its first moments of selected polymers were experimentally determined through GPC-investigations with additional molecular weight detection. In on-line operation discontinuously functioning Ubbelohde-viscometer was used for the determination of degree of polymerization in dependence on elution volume.

The relation between the experimentally determined values and relative kinetic parameters were derived for some polymers prepared by radical mechanism. The relative constants which determines the branching structure in polymer can be now calculated.

From the investigated polymers the effect of chemical nature of monomer units for the branching formation was determined.     

A review of: “Instrumental HPTLC,by W. Bertsch,S. Hara,R. E. Kaiser,and A. Zlatkis,editors, H. Verlag,Heidelberg, West Germany, 1980, 390 pp., cloth bound.”

Abstract

To understand the retention mechanisms involved in reversed-phase micelle chromatography, two models were examined to study the temperature and micelle concentration contribution to the retention process. the first model described the temperature contribution, using the van's Hoff equation, for each of the three equilibria: micelle-to-extra-micelle-mobile-phase, extra-micellar-mobile-phase-to-stationary phase and micelle-to-stationary phase. the second model described the temperature contribution on k' irrespective of the various equilibria involved. It was found that the enthalpy of retention obtained with the second model decreased with increasing micelle concentration. This contradicted a primary assumption in the first model that the equilibrium constants were independent of micelle concentration. No relationship was found between the enthalpy of retention evaluated with either model and the polarity of the partitioned solute molecules. A correlation was found between the entropy of retention and the polarity of these molecules. Fluorescence studies indicated that the micelle solvated molecules were probably located in the core of the micelles which contained other mobile phase components such as 1-propanol and water.     

Determination of Chelating Properties of Detergent Builders with the Calcium Selective Ion Electrode

Abstract

A liquid membrane calcium selective ion electrode was used to measure the free calcium content in equilibrium with calcium chelates. The chelating value, chelating curves, formation constants and equivalent weights of several detergent builders were calculated from these measurements.     

Comparison of calix[n]arenes phosphorylated in the upper and lower rims as applied to extraction of nitrosoruthenium nitrite species

Compared were dialkylcalix[4]phosphine oxides (L) having PO groups in the opposing rims as regards the extraction of [RuNO(NO₂)₄(OH)]²⁻, nonprecious metals (M²⁺), and Ru/M heterometallic complexes of their base. The extraction constants for the ion association {(Na⁺)₂(LH₂O) _r [RuNO(NO₂)₄(OH)]²⁻ and the degree of aggregation of L were calculated. The destruction of (LH₂O) _r upon metal extraction was verified IR-spectroscopically. The stoichiometry was determined and extraction constants were calculated for mono- and binuclear complexes [M _m L _n (NO₃)_2m ] and mononuclear Ru/M species [RuNO(NO₂)₄(OH)ML _n ]. Nonprecious metals form mononuclear ML complexes in the lower rim. The size of the upper rim is responsible for the addition of a second metal nitrate molecule or addition to L or the addition of a second L molecule to the metal. Ru/M complexes with all L are present in an organic phase as two mononuclear species, ML and ML₂. Rationale is given to the selection of extraction systems for recovery of ruthenium from nitrated nitric acid solutions selectively or together with actinides and lanthanides in the form of Ru/M complexes.     

Ligands of low electronegativity in the vsepr model: first row hydrides MH2 and MH3

Skeletal bending potentials are calculated, in the MINDO approximation, for thirteen first row hydrides MH₂, containing six, seven or eight valence electrons, and out-of-plane bending potentials are calculated for nine first row hydrides MH₃ containing seven or eight valence electrons. Both the equilibrium geometries, and the force constants for deformation from linearity for MH₂ or from planarity for MH₃ strongly support an interpretation, in terms of the second order Jahn-Teller effect, of the observed stereochemical inactivity of non-bonding electrons in the presence of ligands of low electronegativity.     

On the validity of the elastic model for the nematic surface anchoring energy

Abstract

The intrinsic uniform and non-uniform contributions to the anisotropic part of the surface energy are considered. Our analysis shows that the uniform part can be separated into an intrinsic and an extrinsic term. The first one is due to the nematic-nematic interaction only, whereas the second one is due to the nematic-substrate interaction. They are found to be of the same order of magnitude (≈1 erg cm²). The non-uniform part takes its origin from the spatial variation of the elastic constants. By means of a semi-microscopic model it is shown that, in the framework of perfect nematic order, the extrapolation length of the elastic origin is microscopic. On the contrary, if the spatial variation of the scalar order parameter is taken into account, simple calculations indicate that the extrapolation length is of the order of the coherence length in the nematic phase.