Inversion of the Kirkwood–Buff Theory of Solutions: Application to Tetrahydrofuran + Aromatic Hydrocarbon Binary Liquid Mixtures

The Kirkwood–Buff (K-B) integrals play an important role in characterizing the intermolecular interactions in liquid mixtures. The interaction is represented by the K-B parameters, G _AA,G _BB, and G _AB, which reflect correlation between like-like and like-unlike species in the mixture. The K-B integrals of binary mixtures of tetrahydrofuran with benzene, toluene, o-xylene, m-xylene, p-xylene and mesitylene at 298.15 K and atmospheric pressure have been computed from the experimental data of ultrasonic speed and density. We have used the similar inverse procedure (as proposed by Ben-Naim) to compute the K-B parameters of the mixture, in which thermodynamic information on mixtures, such as partial molar volumes, isothermal compressibility and experimental data of partial vapor pressures were used. A new route has been incorporated by using regular solution theory in the computation of excess Gibbs energy for obtaining the partial vapor pressures of binary liquid mixtures. The low values of excess entropy, S ^E≈0, obtained for these mixtures indicate the applicability of regular solution theory to the mixtures. The values of the K-B parameter, G _AB, obtained using this procedure indicate that the correlation/affinity between THF and aromatic hydrocarbon molecules follows the order: benzene > toluene > o-xylene > m-xylene > p-xylene > mesitylene, which is in good agreement with the results obtained from the trends exhibited by the excess functions of these mixtures.     

The Effect of Alkane Chain Length on the Liquid–Liquid Critical Temperatures of Oligostyrene/Linear-Alkane Mixtures

Summary. Upper critical solution temperatures (UCSTs) for liquid–liquid demixing in a set of mixtures of linear alkanes (pentane (N ₁=5) to pentacontane (N ₁=50)) with an oligostyrene (1241amu, N ₂=12) are reported. We find strong correlation between the Hildebrand solubility parameters of the alkanes and the UCST. Correlations are developed which enable predictions concerning the miscibility of mixtures of compounds with longer chains.     

Dielectric Studies of Binary Mixtures of some Amines—Aniline and Pyridine—in Nonpolar Solvents—Solute–Solvent Interactions

Abstract

Dielectric constant of binary mixtures of aniline and also pyridine in nonpolar liquids namely benzene, carbon tetrachloride, p-xylene and n-heptane have been measured at 455 kHz for four different temperatures. Eyring's interaction parameter G? based on the significant structure model is calculated in the mixtures using the experimentally determined value of dielectric constant.

The nature of the solvent is found to influence this parameter G? reflecting the non-specific solute-solvent interaction. The calculated value of G? is used for interpreting dipole interaction of solute molecules in the solvent environment.     

Applied Aspects of the γ-Radiolysis of C1–C4 Alcohols and Binary Mixtures on Their Basis

Generalized data on the -radiolysis of aliphatic C₁–C₄ alcohols are summarized. These data can be used for solving practical problems in the related areas of research. In particular, a rate equation that relates the radiation-chemical yield of an 1 : 1 adduct formed from saturated and unsaturated components upon the -radiolysis of a binary system to the concentrations of these components was derived. An equation was obtained for estimating the reaction rate constants of decay of identical hydroxyalkyl radicals in collisions with each other from the reciprocal viscosity (fluidity) of corresponding alcohols. An empirical equation for calculating the concentration of the free (desolvated) form of formaldehyde in alcohol–formaldehyde systems at various temperatures and total formaldehyde concentrations and an equation for evaluating solvent concentrations in these systems were derived.     

Ultrasonic Studies on Molecular Interactions in Binary Mixtures of N-Methyl Aniline with Methyl Isobutylketone, +3-Pentanone, and +Cycloalkanones at 303.15 K

Densities, ρ, viscosities, η, and ultrasonic sound velocities u of pure methyl isobutylketone, diethylketone, cyclopentanone, cyclohexanone, 2-methyl cyclohexanone and those of their binary mixtures with N-methyl aniline were measured at 303.15 K over the entire composition range. These experimental data have been used to calculate the excess volume (V ^E), deviation in ultrasonic sound velocity (?u), isentropic compressibility (κ _s ), intermolecular free length (L _f), excess intermolecular free length ( $ L_{\text{f}}^{\text{E}} $ L f E ), acoustic impedance (Z), excess isentropic compressibility ( $ \kappa_S^{\text{E}} $ κ S E ), deviation in viscosity (?η) and excess Gibbs energy of activation of viscous flow (G ^*E). The viscosity data have been correlated using three equations proposed by Grunberg and Nissan, Katti and Chaudhri, and Hind et al. The excess/deviations have been fitted by Redlich–Kister equation and the results are discussed in terms of molecular interactions present in these mixtures.     

Excess Molar Volumes and Viscosities of Binary Mixtures of Methanol and the Ionic Liquid 4-Methyl-N-butylpyridinium Tetrafluoroborate at 25, 40, and 50°C

Experimental data of densities and viscosities are presented for the system 4-methyl-N-butylpyridinium tetrafluoroborate + methanol at 25, 40, and 50, 323.15 K and ambient pressure using a vibratage-tube densimeter and an Ubbelohde viscometer. Excess molar volumes V ^E and excess logarithm viscosities (ln )^E have been determined. V ^E is negative and (ln )^E positive over the entire mixture composition.     

Densities and Excess Molar Volumes of Binary and Ternary Mixtures Containing Acetonitrile + Acetophenone + 1,2-Pentanediol: Experimental Data,Correlation and Prediction by PFP Theory and ERAS Model

Densities were determined experimentally over the entire range of composition at 298.15 K for the ternary system acetonitrile (1) + acetophenone (2) + 1,2-pentanediol (3) and for the three corresponding binary systems. Excess molar volumes were calculated for the binary and the ternary systems. These results were fitted to variable-degree polynomials. Further, the Prigogine-Flory-Patterson (PFP) theory and Extended Real Associated Solution (ERAS) model were applied to V_m^EV_{m}^{\mathrm{E}} for the binary mixtures of acetonitrile + acetophenone, acetonitrile + 1,2-pentanediol and acetophenone + 1,2-pentanediol, and the findings compared with the experimental results.     

The Relative Reduced Redlich–Kister and Herráez Equations for Correlating Excess Properties of N,N-Dimethylacetamide + Formamide Binary Mixtures at Temperatures from 298.15 K to 318.15 K

Excess molar volumes and viscosity deviations in binary mixtures of N,N-dimethylacetamide with formamide at (298.15, 308.15 and 318.15) K were calculated from experimental density and viscosity data presented in previous work. The density and viscosity data as well as their corresponding derived functions were used to test the applicability of two correlative equations: the reduced Redlich?CKister equation and the recently proposed Herráez equation. Their correlation abilities at different temperatures, and the use of different numbers of parameters, are discussed for the case of limiting experimental data. These relative functions are important to reduce the effect of temperature and, consequently, to reveal the effects of different types of interactions. Correlation between the two Arrhenius parameters of viscosity over the composition domains shows the existence of two distinct behaviors.     

Densities and Volumetric Properties of Butyl Acrylate + 1-Butanol, or +2-Butanol, or +2-Methyl-1-propanol, or +2-Methyl-2-propanol Binary Mixtures at Temperatures from 288.15 to 318.15 K

The densities, ρ, of binary mixtures of butyl acrylate with 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol, including those of the pure liquids, were measured over the entire composition range at temperatures of (288.15, 293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K and atmospheric pressure. From the experimental data, the excess molar volume $ V_{\text{m}}^{\text{E}} $ V m E , partial molar volumes $ \overline{V}_{\text{m,1}} $ V ¯ m,1 and $ \overline{V}_{\text{m,2}} $ V ¯ m,2 , and excess partial molar volumes $ \overline{V}_{\text{m,1}}^{\text{E}} $ V ¯ m,1 E and $ \overline{V}_{\text{m,2}}^{\text{E}} $ V ¯ m,2 E , were calculated over the whole composition range as were the partial molar volumes $ \overline{V}_{\text{m,1}}^{^\circ } $ V ¯ m,1 ° and $ \overline{V}_{\text{m,2}}^{^\circ } $ V ¯ m,2 ° , and excess partial molar volumes $ \overline{V}_{\text{m,1}}^{{^\circ {\text{E}}}} $ V ¯ m,1 ° E and $ \overline{V}_{\text{m,2}}^{{^\circ {\text{E}}}} $ V ¯ m,2 ° E , at infinite dilution,. The $ V_{\text{m}}^{\text{E}} $ V m E values were found to be positive over the whole composition range for all the mixtures and at each temperature studied, indicating the presence of weak (non-specific) interactions between butyl acrylate and alkanol molecules. The deviations in $ V_{\text{m}}^{\text{E}} $ V m E values follow the order: 1-butanol < 2-butanol < 2-methyl-1-propanol < 2-methyl-2-propanol. It is observed that the $ V_{\text{m}}^{\text{E}} $ V m E values depend upon the position of alkyl groups in alkanol molecules and the interactions between butyl acrylate and isomeric butanols decrease with increase in the number of alkyl groups at α-carbon atom in the alkanol molecules.     

Investigations of Molecular Interactions in Binary Mixtures of the Ionic Liquid [Emim][BF<Subscript>4</Subscript>] and <Emphasis Type="Italic">N</Emphasis>-Methylaniline at Temperatures from 293.15 to 323.15 K

Density (ρ) and speed of sound (u) values were measured for the binary mixture of 1-ethyl-3-methylimidazolium tetrafluoroborate ([Emim][BF₄]) and N-methylaniline over the entire range of mole fractions at temperatures from 293.15 to 323.15 K under atmospheric pressure. Using the basic experimental data, various acoustic and thermodynamic parameters were calculated and are discussed with regard to the molecular interactions in the binary systems. The partial molar volumes and partial molar isentropic compressibilities at infinite dilution have also been calculated. The excess values were fitted to Redlich–Kister polynomial equation to estimate the binary coefficients and standard deviation between the experimental and calculated values. Further, the molecular interactions in the binary mixture system are analyzed using the experimental FT-IR spectra recorded at room temperature.     

Thermodynamics of organic mixtures containing amines - III: Molar Excess Volumes at 298.15 K for Tripropylamine +n‐Alkane Systems ‐ Application of the Flory Theory to N,N,N‐Trialkylamine + n‐Alkane Mixtures

Molar excess volumes at 298.15 K and atomospheric pressure for tripropylamine + n-hexane, + n-octane, + n-decane, + n-dodecane or + n hexadecane systems determined from densities measured with an Anton-Paar DMA 602 vibrating-tube densimeter are reported. N,N,N-trialkylamine + n-alkane systems have been studied using the Flory theory. Better results on excess enthalpies are obtained when the difference in size between the mixture components is large.

The dependence of the excess volume at equimolar composition with the length of the n-alkane is correctly described. The simultaneous analysis of the experimental excess volumes and of the excess enthalpies reveal that free volume effects are important in systems formed by triethylamine or tripropylamine and longer alkanes, as well as in those involving tripropylamine or tributylamine and the shorter alkanes.

The Patterson effect is present in the studied mixtures. The more globular amines, triethylamine, tripropylamine or tributylamine are order breakers of the longer alkanes. The amines of very large size, e.g., tridodecylamine, show an ordered structure.     

Photoluminescence of Mn2+ in the Borosulfate Zn[B2(SO4)4] : Mn2+—A Tool to Detect Weak Coordination Behavior of Ligands

The impact of the surrounding ligand field is successfully exploited in the case of Eu²⁺ to tune the emission characteristics of inorganic photoactive materials with potential application in, e.g., phosphor-converted white light-emitting diodes (pc-wLEDs). However, the photoluminescence of Mn²⁺ related to intraconfigurational 3d⁵–3d⁵ transitions is also strongly dependent on local ligand field effects and has been underestimated in this regard so far. In this work, we want to revive the idea how to electronically tune the emission color of a transition metal ion in inorganic hosts by unusual electronic effects in the metal-ligand bond. The concept is explicitly demonstrated for the weakly coordinating layer-like borosulfate ligand in the Mn²⁺-containing solid solutions Zn_1-xMn_x[B₂(SO₄)₄] (x = 0, 0.03, 0.04, 0.05, 0.10). Zn[B₂(SO₄)₄]:Mn²⁺ shows orange narrow-band luminescence at 590 nm, which is an unusually short wavelength for octahedrally coordinated Mn²⁺ and indicates an uncommonly weak ligand field. On the other hand, the analysis of the interelectronic Racah repulsion parameters reveals ionic Mn−O bonds with values close to the Racah parameters of the free Mn²⁺ ion. Overall, this strategy demonstrates that electronic control of the metal-ligand bond can be a tool to make Mn²⁺ a potent alternative emitter to Eu²⁺ for inorganic phosphors.     

Interfacial transfer of Cd2+ assisted by 4′ — morpholino-acetophenone-4-phenyl-3-thiosemicarbazone across the water/1,2-dichloroethane interface

The assisted transfer of heavy metal ions by interfacial complexation with 4′-morpholinoacetophenone-4-phenyl-3-thiosemicarbazone (MAPPT) at the interface between two immiscible electrolyte solutions (ITIES) was studied by cyclic voltammetry. The voltammograms obtained across the water/1,2-dichloroethane interface using the MAPPT ligand in the organic phase shows that the assisted metal ion transfers have different nature for different ions. The quasi-reversible voltammetric peak of the Cd²⁺ ion was obtained and is discussed in detail. The dependence of the half-wave transfer potential on MAPPT concentration showed that the equilibrium is effectively displaced towards a 1:3 (metal:ligand) stoichiometry with an association constant of log β ^o =15.46 (±0.11) for the Cd²⁺ ion, corresponding to the TIC/TID mechanism.      

Efficient Transition‐Metal‐Free Oxidation of Benzylic and Secondary Alcohols to the Carbonyl Compounds Using an N‐Bromosuccinimide/NH4Cl System

The oxidation of a variety of benzylic and secondary alcohols was achieved in excellent yields using an NBS/NH₄Cl system in aqueous acetonitrile (CH₃CN‐H₂O; 7/3 v/v) at 80°C under very mild conditions.     

Complexation of 4′-Nitrobenzo-15-crown-5 with Zn<Superscript>2+</Superscript>, Mn<Superscript>2+</Superscript>, Cr<Superscript>3+</Superscript> and Sn<Superscript>4+</Superscript> Cations in Acetonitrile–Ethanol Binary Mixtures

The complexation reactions of 4′-nitrobenzo-15-crown-5 (4′NB15C5) with Zn²⁺, Mn²⁺, Cr³⁺ and Sn⁴⁺ cations were studied in acetonitrile–ethanol (AN–EtOH) binary solvent mixtures at different temperatures by the electrical conductometry method. The stability constants of the resulting 1:1 complexes were determined from computer fitting of the conductance versus mole ratio data. The results show that the selectivity order of 4′NB15C5 for the metal cations in the AN–EtOH (mol-%AN=76) binary solvent at 298.15 K is: Cr³⁺>Mn²⁺≈Zn²⁺>Sn⁴⁺, but the selectivity order changes with the composition of the mixed solvents. A nonlinear relationship was observed between the stability constants (log ₁₀ K _f) of these complexes and the composition of the AN–EtOH binary solvents. The corresponding thermodynamic parameters (DH_c^o, DS_c^o)(\Delta H_{\mathrm{c}}^{\mathrm{o}}, \Delta S_{\mathrm{c}}^{\mathrm{o}}) were obtained from the temperature dependence of the stability constants using van’t Hoff plots. The results show that the values and also the sign of these parameters are influenced by the nature and composition of the mixed solvents.     

Potentiometric Titration of Na2HAsO4, NaPO3, Na4P2O7, and their Binary Mixtures in NaNO3 Melt at 350°C Using a Novel Solid State Glass/TiO2 as pH Indicator Electrode

A solid‐state glass/TiO₂ electrode was fabricated using a transparent conductive titanium oxide film on a glass substrate. The coating of the glass substrate was achieved by a novel simple chemical vapor deposition (CVD) procedure. This electrode can be used as an indicator electrode in potentiometric acid‐base titration. This electrode behaves reversibly and responds to the oxide ion concentration in molten NaNO₃ · Na₂HAsO₄, NaPO₃, Na₄P₂O₇, and their binary mixtures were potentiometrically titrated with Na₂O₂ as titrants in molten NaNO₃ at 350°C, using the above mentioned indicator electrode.     

Application of the Ru(bipy)2(dpp)2+ / C2O4 2− electrochemiluminescence reaction to the determination of phenol

The electrochemiluminescence (ECL) of the ruthenium di(2,2′-bipyridine)- (4,7-diphenyl-1,10-phenanthroline) complex (Ru-bipy-dpp) produced on a glassy carbon electrode was studied by cyclic voltammetry. The anodic oxidation of Ru-bipy-dpp produces ECL in the presence of oxalate in oxygen-free aqueous solutions. Threefold ECL efficiencies were obtained for Ru-bipy-dpp relative to Ru(bipy)₃ as a standard. The ECL of Ru-bipy-dpp is quenched by both oxygen and phenol. The luminescence intensity was proportional to the concentration of phenol in the range of 5–100 μM. At a phenol concentration of 100 μM, the ECL of Ru-bipy-dpp peaking at 597 nm was completely quenched. Correspondence: Dan Xiao, College of Chemistry and Chemical Engineering, Sichuan University, Chengdu 610065, P.R. China     

Secondary α-deuterium kinetic isotope effects in [2+4] cycloaddition of (E)-2-phenylnitroethene to cyclopentadiene

Abstract  

Secondary α-deuterium kinetic isotope effects confirm that [2+4] cycloaddition between (E)-2-phenylnitroethene and cyclopentadiene occurs in concerted manner, on both the pathway leading to 6-endo-phenyl-5-exo-nitronorbornene and the pathway leading to the corresponding 6-exo-phenyl-5-endo-nitro isomer. According to Hammond terminology the transition states on competitive pathways should be considered in terms of symmetrical early states.     

Stereoselective routes to substituted β-amino carbonyl compounds via heterodiene [4π+2π] cycloadditions of auxiliary-based C2 symmetric ketene acetals

Heterodiene [4π+2π] cycloadditions of (S,S)-4,5-diaryl-2-methylene-1,3-dioxolanes 1 to a series of β-amido-α,β-unsaturated carbonyl compounds are diastereoselective (d.r.≥4:1). The products can be purified by trituration or crystallisation and hydrolysed with acid to generate the corresponding β-amido carbonyl compounds, the overall sequence effecting an auxiliary-based enantioselective conjugate addition of an acetate enolate, leading to β-aminoacid derivatives.     

A comparison of two effective chiral auxiliaries—(2R)-bornane-10,2-sultam and (2R)-bornane-10,2-cyclohydrazide—using the [4+2] cycloaddition of cyclopentadiene to their N,N′-fumaroyl derivatives

A correlation between the solvent polarity and the logarithm of the diastereoisomer ratio (dr) was found for the uncatalyzed [4+2] cycloaddition of cyclopentadiene to N,N′-fumaroyldi[(2R)-bornane-10,2-(2′-phenyl-pyrazol-3′-one)]. Using the Abboud–Abraham–Kamlet–Taft parameters, predictive values for this method resulted in an optimum diastereoisomeric excess (de) of more than 97% in hexane. Implications for the stereochemical course of the reaction as well as a comparison with the analogous (2R)-bornane-10,2-sultam auxiliary are discussed.