Complexation of Calix[4]arenephosphonous Acids with 2,4-Dichlorophenoxyacetic Acid and Atrazine in Water

In capillary electrophoresis using poly(vinyl sulfate), added to sample solutionsand running buffers, the signal of Rhoda-mine 6G (R6G) is shaped like a squarewave. When -, -, or -cyclodextrin (-, -,or -CD) has further been added to the running buffers as well as samplesolutions, the intensity of the square-wave type signal of R6G has been enhanced,accompanied by narrowing of the signal width. The migration time of the risingedge of the square-wave type signal has been very slightly delayed by the additionof CD. These findings exhibit the formation of inclusion complexes of R6G withCDs. From the analyses of the variations in signal width with the concentration ofCD, the equilibrium constants for the formation of the 1:1 inclusion complexes ofR6G with -, -, and -CDs have been evaluated to be 245,210, and 302 M^-1, respectively, although the equilibrium constants could not be estimated using a conventional procedure based on electrophoretic mobility, inwhich poly(vinyl sulfate) was not added. The values of the equilibrium constants for- and -CDs are comparable to those obtained from the absorbancechanges in spectrophotometry, whereas the value for -CD is about four timesgreater than that obtained from the absorbance change.     

UV-spectroscopic study of complex formation by certain cycloolefins with tetracyanoethylene and molecular iodine

UV spectroscopy of charge-transfer complexes (CTCs) with tetracyanoethylene (TCE) and iodine has been used to study the relative donor ability of mono- and bicycloolefins and the stability of the CTCs. The donor ability of bicycloolefins, characterized by _CT(TCE), increases with increase in ring strain. The equilibrium constants for complex formation of bicycloolefins with TCE are linearly related to the rate constants of the reaction of epoxidation by tert-butyl hydroperoxide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1314–1318, June, 1990.     

Metal - MoOx interaction and hydrodesulfurization activity of PdMo and PtMo catalysts

The ratios of the benzene/cyclohexane and of toluene/cyclohexane adsorption equilibrium constants were determined from the dehydrogenation rates of cyclohexane in its binary mixtures with benzene and toluene, respectively. The calculated adsorption constant ratios of toluene/benzene indicate a PdMo and a MoPt electron transfer. The opposite direction of the two electron transfers is compared with XPS and catalytic activity data.     

Solvatochromic parameters for binary mixtures and a correlation with equilibrium constants. Part I. Dioxane-water mixtures

The values of the solvatochromic parameters and were determined at 25°C for dioxane-water mixtures from 0 to 100% of dioxane. These values as well as those of the Reichardt polarity parameter E _T (30) and the polarity-polarizability ^* are correlated with acid dissociation constants and other equilibrium constants in solvent mixtures of the same composition. As a general rule, two linear zones with different slopes are obtained, one zone covering water-rich solutions, and the other dioxane-rich solutions. The change in behavior takes place at about 55% (v/v) dioxane for all equilibria studied. A fit of pK to an equation of the multiparametric form proposed by Kamlet and Taft shows in most cases a linear dependence on ^* alone, in other cases a dependence on ^* and .     

Thermodynamic parameters of free radical-dimer equilibria in phenylindandione derivatives

Conclusions Measurements of the thermodynamic parameters of the free radical-dimer equilibrium in benzene for 2,2-bis[R-2-(p-dimethylaminophenyl)indan-1,3-diones] with different substituants R on the phthaloyl ring have been carried out. The equilibrium constants satisfy the Hammett equation (p=0.87, benzene, 20C). The bond breaking energy of the central C₂–C₂' bond in the dimers amounts to 18–20 kcal/mole The extinction coefficients of the 2-aryl-indan-1,3-dione-2-yl radicals in benzene have been determined. The long-wave band of the radicals displays thermo- and solvatochromism.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1237–1243, June, 1988.     

Complexation of copper(II) with β-<Emphasis Type="Italic">tert</Emphasis>-butyl L-aspartate in the presence of anionic surfactant

Complexation of copper(II) with -tert-butyl L-aspartate in aqueous solutions of the anionic surfactant, sodium dodecyl sulfate, was studied by spectrophotometry, followed by mathematical processing of the results. Compositions of complexes and equilibrium constants of their formation reactions were determined.Translated from Kolloidnyi Zhurnal, Vol. 66, No. 6, 2004, pp. 860–861.Original Russian Text Copyright © 2004 by Vladimirova, Vladimirov.     

Thermodynamic and 13C NMR Studies of the Inclusion Complexes of α- and β-Cyclodextrins with Cyano- and Nitrophenols in Aqueous Solution

Equilibrium constants for the formation of 1 : 1 inclusioncomplexes of -cyclodextrin (-CD) with neutral and anionic phenol derivatives (3- and 4-cyanophenols and 3- and 4-nitrophenols) have been evaluated at 5, 12, 25, and 35 °C by means of spectrophotometry. Similarly, the equilibrium constants have been determined for the inclusion complexes of-cyclodextrin (-CD) with the phenols. Enthalpy and entropy changes for the formationof the inclusion complexes have been estimated from the temperature dependences of theequilibrium constants. With -CD, the enthalpy andentropy changes for the anionic species have been found to be more negative than those for the neutral ones, except for 4-cyanophenol, suggesting that the inclusion complexes of the anionic species are more rigid than those of the neutral species. From analyses of chemical shift differences in ¹³C NMR spectra of 3- and 4-cyanophenolsand 3- and 4-nitrophenols in aqueous solutions with and without CDs, a nitro ora cyano group has been found to be first bound to the - and -CD cavities.     

Molecular recognition as shown by the solvent extraction of (R)- and (S)-[α-(1-naphthyl)ethyl] ammonium picrate or orange 2 by chiral pyridino-crown ethers

A solvent extraction technique was used to determine equilibrium constants for the reactions occurring when an aqueous phase containing [-(1-naphthyl)ethyl]ammonium ions [(R)- and (S-isomers] is equilibrated with a chloroform phase containing chiral substituted pyridino-18-crown-6 ligands. Selectivity coefficients and equilibrium constants for the interactions in chloroform solutions were calculated. The existence of two different types of ion pairs separated by the macrocycle molecule was detected from the UV spectra. One ion pair has a nearly complete separation of the picrate anion from the protonated amine by the ligand. The other has the picrate ion only partly separated from the cation by the macrocycle.     

Thermodynamics of Cm(III) in Concentrated Salt Solutions: Carbonate Complexation in NaCl Solution at 25°C

The carbonate complexation reactions of Cm(III) were studied by time-resolved laser fluorescence spectroscopy in 0–6 m NaCl at 25°C. The ionic strength dependence of the stepwise formation constants for the carbonato complexes Cm(CO₃) _n ^3–2n with n = 1, 2, 3, and 4 is described by modeling the activity coefficients of the Cm(III) species with Pitzer's ion-interaction approach. Based on the present results and literature data for Cm(III) and Am (III), the mean carbonate complexation constants at I = 0 are calculated to be: log ₁₀₁ ^o =8.1 ±0.3, log ₁₀₂ ^o =13.0 ± 0.6, log ₁₀₃ ^o =15.2 ± 0.4, and log ₁₀₄ ^o =13.0 ± 0.5. Combining these equilibrium constants at infinite dilution and the evaluated set of Pitzer parameters, a model is obtained, that reliably predicts the thermodynamics of bivalent actinide An(III) carbonate complexation in dilute to concentrated NaCl solution.     

Novel enhancement effect of a proton donor on chelate extraction: Extraction of iron(III) with acetylacetone and 3,5-dichlorophenol

Effect of 3,5-dichlorophenol (DCP) on the extraction of Fe(III) with acetylacetone (Hacac) in nonpolar organic solvents has been studied. It is found that a mixture of Hacac and DCP in heptane gives much higher extraction of Fe(III) than Hacac alone. Such novel enhancement effect is ascribable to the association of tris(acetylacetonato)iron(III) [Fe(acac)₃] with DCP in the organic phase by hydrogen bonding. Association of Hacac with DCP has also been investigated and the intrinsic extraction equilibrium of Fe(III) is analyzed by using the equilibrium concentration of free Hacac and DCP. The association complexes are found to be Fe(acac)₃ · n DCP (n=1, 2, 3) in heptane, and the overall association constants (_{ass, n}) are determined to be log _{ass, 1} = 3.41, log _{ass, 2}, = 5.97 and log _{ass, 3}, = 7.50.     

Spin-lattice relaxation behaviour of water in cellulose materials in relation to the tablet forming ability of microcrystalline cellulose particles

Medical tablet forming ability of microcrystalline cellulose (MCC) was investigated in relation to the mobility of water molecules in MCC particles. For this purpose, the spin-lattice relaxation time T1 of water in the system was measured by 1H-NMR. Over a wide range of water contents (0.02 H2O/cellulose (g/g) 1.79), two different T1 (T1,l and T1,s) values were observed for water in each MCC sample. Below the equilibrium water content, water having these two different T1 values exchange with each other in an MCC particle reaching an equilibrium state within a given time scale (equilibrium constant K). The T1,l, T1,s and K values for water in MCC, estimated at the equilibrium water content, showed fairly good correlations with the hardness of the tablets made by the MCC samples. Sample with a shorter T1, or larger K tended to have a stronger tablet forming ability. In the spin-spin relaxation time T2 measurements for protons in an MCC/D2O system, two T2 components originating from the glassy cellulose solid (T2,G) and the swelling region (T2,l) were observed. It was found that the mole fraction xL of protons with T2,L in the system exhibits a clear linear correlation with K. From these results, a structural model for the distribution of water in MCC particles was propoed by taking the surface of each microfibril and the disordered region within the microfibril into consideration     

Liquid-Vapor Equilibrium and Ionization of HCl in the System HCl-H2SO4-H2O at 298 K

The equilibrium pressures and compositions of the vapor over HCl-H₂SO₄-H₂O solutions with a low content of HCl and several fixed concentrations of H₂SO₄ were measured by the flow method at 298 K. The semiconcentration values of the mixed dissociation constants of HCl were calculated and extrapolated to infinite dilution.     

Protonation constants of α-alanine in electrolyte mixtures at constant ionic strength

The stoichiometric acid-base equilibrium constants for -alanine in tetraethylamonium iodide-potassium nitrate solutions were determined at a constant ionic strength of 1.4 m at 25°C. The results obtained are discussed on the basis of the Friedman and the Pitzer model for electrolyte mixtures.     

Nitroso group transfer from N-nitrososulfonamides to thiolate ions. Intrinsic reactivity

The nitroso group transfer from N-nitrososulfonamides to thiolate ions was studied. Based on the results, the reaction rate is strongly dependent on the nature of the leaving group (αlg≈−1.30), but virtually independent of the basicity of the thiol (βnuc≈0.10). This dependence is ascribed to the presence of a nucleophile desolvation equilibrium (βd) that is followed by the attack of the thiolate ion on the nitroso group via a concerted mechanism. The equilibrium constants for the loss of a nitroso group from a nitrosothiol and an N-nitrososulfonamide were used to obtain the equilibrium constants for the different reactions involved. By using rate-equilibrium correlations, the parameters , βd, and were obtained.     

Solubility of Crystalline Calcium Isosaccharinate

The solubility of calcium isosaccharinate Ca(ISA)₂(c) was determined at 23°C as a function of pH (1–14) and calcium ion molality (0.03–0.52). The similarity of solubility from the over- and undersaturation directions for different equilibration periods indicated that equilibrium in these solutions was reached rapidly (< 7 days) and that these data can be used to develop thermodynamic equilibrium constants. The solubility data were interpreted using the Pitzer ion–interaction model. The logarithms of the thermodynamic equilibrium constants determined from these data were 1.30 for the dominant reaction at pH < 4.5 [Ca(ISA)₂(c) + 2H⁺ Ca²⁺ + 2HISA(aq)], and –2.22 for the dominant reaction at 4.5 [Ca(ISA)₂(c)+ Ca(ISA)₂(aq)]. In addition, the logarithm of the dissociation constant of HISA [HISA(aq) ISA- + H⁺] was calculated to be –4.46.     

Dipole moments of halogenonitroalkanes

The empirical dependences of the values of the dipole moments of different types of halogenonitroalkanes on the o^*, _R ⁰ constants and the electronegativity of the halogens and on the ^* constants of the hydrocarbon radicals were established.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 626–628, March, 1991.     

Adsorption modeling of antimony(V) on diphenylthiocarbazone loaded polyurethane foam

The uptake behavior of Sb(V) onto diphenylthiocarbazone (H2DZ) loaded polyurethane foam (PUF) from aqueous solutions of different acids in the presence of KI have been studied. The maximum adsorption was found from 0.5N HNO₃ containing 0.2M KI. The maximum equilibrium was achieved within twenty minutes shaking time. The sorption behavior followed the Freundlich and Langmuir adsorption isotherms. The Freundlich constants 1/n and K_f are 0.57 and 3.26^.10^-2 mol^.g^-1, respectively. The Langmuir constants M and b are 2.18^.10^-4 mol^.g^-1 and 2.4^.10⁴ l^.g^-1, respectively. The value of sorption free energy (E) evaluated from D-R isotherm is 10.8 kJ^.mol^-1 indicating the ion exchange type chemisorption of Sb(V) on H2DZ loaded PUF. The thermodynamic parameters of enthalpy (H), entropy (S) and Gibbs free energy (G) have also been investigated and found to be -51.8 kJ^.mol^-1, -127.3 J^.mol^-1.deg^-1 and -13.8 kJ^.mol^-1, respectively. The negative values of (H) and (G) indicate that the sorption is exothermic and spontaneous in nature. The effect of anions and cations and sorption mechanism are discussed.     

Hydrolysis of Protactinium(V). III. Determination of Standard Thermodynamic Data

Hydrolysis constants of protactinium(V) at tracer scale were deduced from the variations of partition coefficient of Pa(V) in the system: TTA/toluene/Pa(V)/H₂O/H⁺/Na⁺/ClO^– ₄, as a function of TTA and proton concentrations, ionic strength (0.1 3 M), and temperature (10 60°C). Extrapolations of theses constants to zero ionic strength were performed using the SIT model. Standard thermodynamic data (under atmospheric pressure) related to the two hydrolysis equilibria involved, were derived from the temperature dependence of the hydrolysis constants at infinite dilution.     

The effects of cyclodextrin inclusion of the ferrocenemonocarboxylate anion on the kinetics of its oxidation by bis(pyridine-2,6-dicarboxylato)cobaltate(III) in aqueous solution

The effects of -, -, dm-(heptakis(2,6-di-O-methyl)--) and -cyclodextrins (CD) on the kinetics of the electron-transfer reaction of the ferrocenemonocarboxylate anion (FCA^–) with bis(pyridine-2,6-dicarboxylato)cobaltate(III) have been investigated in aqueous solution (0.20 M Na₂HPO₄, pH 9.2) at 25.0°C. Substantial decreases in the rate constants for the electron-transfer reactions were observed upon cyclodextrin inclusion of the reductant, due to an increase in the FCA^0/– reduction potential and to the insulation of the reductant from oxidant. The inclusion stability constants for {FCA·CD}^– were evaluated from the¹H NMR and kinetic data, and the order of the stability constants was found to be -CDdm-CD-CD>-CD.