The excess molar volumes and enthalpies of (N-methyl-2-pyrrolidinone + an alcohol) atT = 298.15 K and the application of the ERAS theory

Excess molar volumes V_m^EatT =  298.15 K and atmospheric pressure are reported for (N -methyl-2-pyrrolidinone  +  propan-2-ol, or butan-1-ol, or butan-2-ol, or 2-methylpropan-1-ol ). TheV_m^E have been calculated from measured values of density using the vibrating tube technique. The results are discussed in terms of the hydrogen bonding and other intermolecular association. Excess molar enthalpiesH_m^E at T =  298.15 K and atmospheric pressure are reported for (N -methyl-2-pyrrolidinone  +  propan-1-ol, or propan-2-ol, or butan-1-ol, or butan-2-ol, or 2-methylpropan-1-ol). The H_m^Ehave been obtained using flow calorimetry. The experimental results have been correlated and compared with the results from the Extended Real Associated Solution (ERAS) theory. The parameters adjusted to the mixtures properties are two cross association parameters and the interaction parameter responsible for the exchange energy of the van der Waals interactions. Self-association parameters of the alcohols and NMP are taken from the literature.     

Thermodynamic and acoustical properties of mixtures <Emphasis Type="Italic">p</Emphasis>-anisaldehyde—alkanols (C<Subscript>1</Subscript>–C<Subscript>4</Subscript>)—2-methyl-1-propanol at 303.15 K

The density, viscosity and speed of sound of pure p-anisaldehyde and some alkanols, for example, methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol, 2-methylpropan-1-ol, and the binary mixtures of p-anisaldehyde with these alkanols were measured over the entire composition range at 303.15 K. From the experimental data, various thermodynamic parameters such as excess molar volume (V^E), excess Gibbs free energy of activation (ΔG*^E), and deviation parameters like viscosity (Δη), speed of sound (Δu), isentropic compressibility (Δκ_s), are calculated. The excess as well as deviation parameters are fitted to Redlich—Kister equation. Additionally, the viscosity data for the systems has been used to correlate the application of empirical relation given by Grunberg and Nissan, Katti and Chaudhari, and Hind et al. The results are discussed in terms of specific interactions present in the mixtures.     

Study of molecular interactions in the polar binary mixtures of N-methyl aniline and alcohols,using excess dielectric and thermodynamic parameters

Molecular interactions between the polar systems N-methyl aniline and alcohols (propan-1-ol/propan-2-ol) for various mole fractions at different temperatures are studied by determining the dielectric permittivity using LF impedance analyzer, Microwave bench and Abbe’s refractometer in radio, microwave and optic frequency regions respectively. The dipole moment, excess dipole moment, excess Helmholtz energy, excess permittivity, excess inverse relaxation time and excess thermodynamic values are calculated using experimental results. The optimized geometry, harmonic vibrational wave numbers and dipole moments of pure and equimolar binary mixtures have been calculated theoretically from the ab initio Hartree–Fock (HF) and Density Functional Theory (DFT – B3LYP) methods with 6-31+G¹ and 6-311+G⁷ basis sets using Spartan 08 modelling software. Conformational analysis of the formation of hydrogen bond in the equimolar binary mixture systems of N-methyl aniline and alcohols (propan-1-ol/propan-2-ol) is supported by experimental FT-IR spectra. The calculated wave numbers and dipole moments agree well with the experimental values. Further, the correlations among the parameters are discussed in detail.     

Structure and molecular interactions in {ethanol + (propan-1-ol/propan-2-ol)} mixtures at 303.15 K

In view of industrial importance of binary {ethyl alcohol + (propan-1-ol/propan-2-ol)} mixtures, the densities (ρ) and refractive indices (n _D ) of these alkanols mixtures were measured for different compositions at 303.15 K. Molar volumes (V _m) and excess molar volumes (V ^E) of these binary mixtures were calculated from experimental density data of pure solvents and solvents mixtures. The measured refractive index and density data was used to calculate specific refractions (R _D ), molar refractions (R _M) and apparent molar refractions (R _{φ, i} ) of binary mixtures. From mole fraction dependence of apparent molar refractions, the limiting apparent molar refractions (R _{φ, i} ^○ ) of propan-1-ol and propan-2-ol have been determined. The graphical values of R _{φ, i} ^○ for propan-1-ol and propan-2-ol were found to be 9.5664 and 7.405 cm³ mol^?1 respectively. Structural changes, geometrical fittings and molecular interactions in binary mixtures of these alkanols have been discussed.     

Static permittivities of ethanol mixtures with isomers of propanol and butanol at temperatures from 288.15 to 308.15 K

The relative permittivities of five binary mixtures of ethanol with propan-2-ol, butan-1-ol, butan-2-ol, 2-methylpropan-1-ol and 2-methylpropan-2-ol are reported for twenty-one mole fractions over the entire concentration range at 288.15, 293.15, 298.15, 303.15 and308.15 K. The excess static permittivity, the permittivity temperature coefficient (?lnε _r/?T) and its excess values were calculated. The excess parameters were fitted to the Redlich–Kister polynomial equation. The results were used in the analysis of hydrogen-bond inter molecular interactions occurring in the alcoholic binary mixtures having different natures of their constituents with varying carbon chain lengths.     

Solvent effects on kinetics of an heteroatomic nucleophilic substitution reaction in ionic liquid and molecular solvents mixtures

Rate constants, k _A, for the aromatic nucleophilic substitution reaction of 2-chloro-3,5-dinitropyridine with aniline were determined in different compositions of 2-propanol mixed with hexane, benzene, and 2-methylpropan-2-ol and 1-ethyl-3-methylimidazolium ethylsulfate ([Emim][EtSO₄]) with dimethyl sulfoxide at 25°C. The obtained rate constants of the reaction in pure solvents are in the following order: 2-methylpropan-2-ol > dimethyl sulfoxide > 2-propanol > hexane > benzene > [Emim][EtSO₄]. Molecularmicroscopic solvent parameters corresponding to the selected binary mixtures were utilized to study the kinetics of a nucleophilic substitution reaction in order to investigate and compare the effects of the solvents on a chemical process. The influence of solvent parameters including normalized polarity (E _T ^N ), dipolarity/polarizability (π*), hydrogen bond donor acidity (α), and hydrogen bond acceptor basicity (β) on the second-order rate constants were investigated and multiple linear regressions gave much better results with regard to single parameter regressions. The dipolarity/polarizability of media has a positive effect in all mixtures regarding zwitterionic character of the reaction intermediate and the hydrogen bond acceptor basicity of the solvent by stabilizing of activated complex increases the reaction rate.     

Oxidation of alcohols by chlorine dioxide in organic solvents

The kinetics of oxidation of a series of alcohols (propan-2-ol, 2-methylpropan-1-ol, butan-1-ol, butan-2-ol, 3-methylpentan-1-ol, heptan-4-ol, decan-2-ol, cyclohexanol, borneol) by chlorine dioxide in organic solvents was studied using spectrophotometry. The reaction is described by the second-order rate equation w = k[ROH][ClO₂]. The rate constants were measured in the range of 10–60 °C, and the activation parameters of the processes were calculated. The products were identified, and the yields were determined.     

Topological investigations of the molecular species and molecular interactions that characterize pyrrolidin-2-one + lower alkanol mixtures

Molar excess volumes, V^E, molar excess enthalpies, H^E, and speeds of sound data, u, of pyrrolidin-2-one (i) + ethanol or propan-1-ol or propan-2-ol or butan-1-ol (j) binary mixtures have been determined over entire composition range at 308.15 K. The observed speeds of sound data have been utilized to predict excess isentropic compressibilities, of the investigated binary mixtures. The observed excess thermodynamic properties V^E, H^E and have been analyzed in terms of Graph theory. The analysis of V^E data by the Graph theory suggests that pyrrolidin-2-one exists mainly as a mixture of cyclic and open dimer; ethanol as a mixture of dimer and trimer; butan-1-ol and propan-2-ol as mixture of monomer and dimer and propan-1-ol as a dimer in the pure state, and their mixtures contain 1:1 molecular complex. The IR studies lend additional credence to the nature and extent of interactions for the proposed molecular entities in the mixtures. Also, it has been observed that V^E, H^E and values predicted by the Graph theory compare well to with their corresponding experimental values.     

Chemiluminescence parameters of peroxynitrous acid in the presence of short-chain alcohols and Ru(bpy)<Stack><Subscript>3</Subscript><Superscript>2+</Superscript></Stack>

The chemiluminescence behaviour and mechanism of peroxynitrous acid and Ru(bpy)₃²⁺ were studied in the presence of short-chain alcohols (methanol, ethanol, propan-1-ol, propan-2-ol, butanol, 2-methylpropan-1-ol, pentanol). It was found that the chemiluminescence intensity of peroxynitrous acid and Ru(bpy)₃²⁺ system could be significantly enhanced by these seven short-chain alcohols. The maximum chemiluminescence wavelength of 608 nm of [Ru(bpy)₃²⁺]* in the excited state was attributed to the reaction between Ru(bpy)₃²⁺ and dihydroxyalkyl radicals which were generated during the redox course of peroxynitrous acid and alcohols. In addition, the chemiluminescence signals of the system presented depended largely on the solubility and branched-chain structure as well as the length of carbon chain. The analytical characteristics and parameters of the peroxynitrous acid/Ru(bpy)₃²⁺/alcohols chemiluminescence system were investigated under optimum conditions.     

Hydrogen-bonded complexes of 1-chloro-2-methylpropan-2-ol with ketones

The interaction of 1-choro-2-methylpropan-2-ol (CMP) with acetone and methyl ethyl ketone was examined in dilute carbon tetrachloride solution. The strengths of the hydrogen-bonded complexes were compared with those of the corresponding complexes of trimethyl carbinol and 1,1,1-trichloro-2-methyl-propan-2-ol with ketones. The aim was to explain the inductive effect of the chlorine atom on the strength of carbinol-ketone hydrogen-bonded complexes. The monomer IR band of CPM appears in solution as a composite of five sub-bands, signifying that many conformers are present; this was confimed by quantum chemical calculations. Chlorine substitution increases the strength of the hydrogen bond.     

Synthesis and biological activity of 1-(aryloxy)-3-(6-chloro-4,4-dimethyl-1,2,3,4-tetrahydroisoquinolin-2-yl)propan-2-ols

Treatment of 1-(4-chlorobenzylamino)-2-methylpropan-2-ol with concentrated sulfuric acid at 0°C gave 6-chloro-4,4-dimethyl-1,2,3,4-tetrahydroisoquinoline which reacted with (aryloxymethyl)oxiranes to afford new propan-2-ol derivatives of the tetrahydroisoquinoline series, 1-(aryloxy)-3-(6-chloro-4,4-dimethyl-1,2,3,4-tetrahydroisoquinolin-2-yl)propan-2-ols. Some of the synthesized compounds or their hydrochlorides showed moderate adrenergic blocking and sympatholytic activities.     

Excess enthalpies for mixtures of cyclohexanone with isomeric propanols and butanols at 298.15 K

Excess enthalpies (H ^E ) for mixtures of cyclohexanone with propan-1-ol. propan-2-ol, butan-1-ol, butan-2-ol and 2-methyl propan-1-ol at 298.15 K have been measured over the entire composition range. All mixed endothermically with the maximum values ofH ^E occurring at equimole fraction. Comments about the molecular interactions contributing to the excess enthalpies of a cyclic ketone + an alcohol are made on the basis of these results.     

Investigations on Binary Mixtures of Propan-2-ol with Methyl Benzoate and Ethyl Benzoate

The molecular interactions between the polar systems propan-2-ol with alkyl benzoates (methyl benzoate and ethyl benzoate), for various mole fractions and different temperatures, were studied by determining the dielectric permittivity using a LF impedance analyzer and Abbe’s refractometer in the static and optical frequency regions, respectively. The effective Kirkwood correlation factor, corrective Kirkwood correlation factor, dipole moment, excess dipole moment, and excess Helmholtz free energy were calculated using the experimental data. Hamiltonian quantum mechanical calculations (ab initio and semiempirical) were performed using PC Spartan and Argus lab Modeling software for both pure and equimolar binary systems of propan-2-ol with alkyl benzoates.     

Excess molar enthalpies of R-fenchone + propan-1-ol or +propan-2-ol. Modeling with COSMO-RS and UNIFAC

In this paper, experimental excess molar enthalpies for the binary mixtures of R-fenchone with propan-1-ol or propan-2-ol, at four temperatures (283.15, 298.15, 313.15 and 328.15) K and atmospheric pressure are reported over the entire composition range. They have been fitted to the Redlich–Kister equation at each temperature. Excess molar enthalpies are positive in all cases, being greater for the mixture with propan-2-ol than for the mixture with propan-1-ol. These positive values of the excess enthalpy suggest the predominance of the effect due to hydrogen bond breaking over the interaction between dissimilar molecules in the mixture. Finally UNIFAC (Dortmund) method and the Quantum Continuum Method COSMO-RS have been used to predict the excess molar enthalpies. Better predictions are obtained in the case of UNIFAC model.     

Excess Molar Volumes, Excess Molar Enthalpies and Excess Isentropic Compressibilities of 1-Methyl Pyrrolidin-2-one with Water and Propanols

Excess molar volumes V ^E, excess molar enthalpies H ^E, and speeds of sound u for 1-methyl pyrrolidin-2-one (1) + water or propan-1-ol or propan-2-ol (2) binary mixtures have been measured over the entire composition range (at 308.15 K) using a dilatometer, calorimeter and interferometer. Speeds of sound data, u, of (1 + 2) binary mixtures have been utilized to determine excess isentropic compressibilities, $ \kappa_{S}^{\text{E}} $ . The observed V ^E, H ^E and $ \kappa_{S}^{\text{E}} $ data have been analyzed in terms of (1) Graph theory (which involves the topology of the constituents of mixture), and (2) the Prigogine–Flory–Patterson theory. Analysis of V ^E data in terms of Graph theory suggests that 1-methyl pyrrolidin-2-one, water, propan-1-ol, and propan-2-ol exist as associated molecular entities. IR studies lend additional support to the proposed molecular entities in (1 + 2) mixtures. It has been observed that V ^E, H ^E and $ \kappa_{S}^{\text{E}} $ values predicted by Graph theory compare well with their corresponding experimental values.     

Synthesis, structures and reactions of some metallocene alcohols

E-1-Ferrocenyl-4,4-dimethylpent-2-ene-1-one has been synthesised from the Friedel-Crafts acylation of ferrocene with E-3-tert-butylacryloylchloride and converted to 1-ferrocenyl-3-chloro-4,4-dimethylpentan-1-one using ethereal hydrogen chloride. This new chloro ketone has been converted into three new ferrocene alcohols: 1-ferrocenyl-3,4-dimethyl-4-hydroxypentan-1-one, 1-ferrocenyl-3-chloro-4,4-dimethylpentan-1-ol, and 2,2,6,6-tetramethyl-3-ferrocenyl-5-chloroheptan-3-ol. A new dinuclear ferrocene derivative, E,E-2,2,9,9-tetramethyl-5,6-diferrocenyl-deca-3,7-diene, was isolated after treatment of 1-ferrocenyl-3-chloro-4,4-dimethylpentan-1-ol with acidic alumina; its structure was confirmed by X-ray crystallography, whilst electrochemistry revealed metal-metal interactions of similar magnitude to those seen for other 1,2-bis(ferrocenyl)ethane derivatives. Crystal structures have also been determined for 2,2,6,6-tetramethyl-3-ferrocenyl-5-chloroheptan-3-ol, rac-1-hydroxy[3]ferrocenophane, rac-1S,3S-1,3-diphenyl-1-hydroxy[3]ferrocenophane, and of rac-1,1^′-diphenyl-1,1^′-(1,1^′- ruthenocenediyl)dimethanol and show an intramolecular Cl?H-O hydrogen bond, a tetramer based on O?H-O hydrogen bonds, no hydrogen bonding, and a dimer with inter- and intramolecular O?H-O hydrogen bonds, respectively.     

Experimental and predicted excess molar enthalpies of binary mixtures containing 2,2′-oxybis[propane], benzene,butan-1-ol, 2-methylpropan-1-ol, 2-methyl-2-ene-1-propanol at 303.15 K

Excess molar enthalpies H^E have been measured for liquid binary mixtures of 2,2′-oxybis[propane] (diisopropylether ‘DIPE’), or, benzene + butan-1-ol, +2-methylpropan-1-ol (isobutanol), +2-methyl-2-ene-1-propanol (isobutenol), +n-heptane at 303.15 K and constant pressure using a C80, Setaram calorimeter. A Redlich–Kister type equation was used to correlate experimental results.     

Crystal structures of copper(II) and nickel(II) complexes with 1,3-bis(3,5-di-tert-butylsalicylideneamino)propan-2-ol

Mononuclear copper(II) and nickel(II) complexes with 1,3-bis(3,5-di-tert-butylsalicylideneamino)propan-2-ol (H₃L) of the general formula [M(HL)] were obtained and structurally characterized. It was demonstrated that the presence of the tert-butyl groups precludes intermolecular hydrogen bonding in the crystals of the complexes and that their molecules are only linked by hydrophobic interactions.     

Thermodynamic interactions in binary mixtures of anisole with ethanol, propan-1-ol, propan-2-ol, butan-1-ol, pentan-1-ol, and 3-methylbutan-1-ol at T = (298.15, 303.15, and 308.15) K

In this paper, excess thermodynamic functions have been computed from the measured values of density, viscosity, and refractive index at T = (298.15, 303.15, and 308.15) K, ultrasonic velocity at T = 298.15 K over the entire mixture composition range of (anisole with ethanol, propan-1-ol, propan-2-ol, butan-1-ol, pentan-1-ol, or 3-methyl butan-1-ol). Excess molar volume, V^E has been calculated from densities, whereas deviations in viscosity, Δη, were computed from the measured viscosities. From ultrasonic velocities, isentropic compressibilities were calculated, from which deviations in isentropic compressibility, Δk_s have been computed. Lorenz-Lorentz mixture rule was used to compute molar refractivity, R from refractivity index data and from these data, deviations in molar refractivity, ΔR have been computed. Computed thermodynamic quantities have been fitted to Redlich and Kister polynomial equation to derive the coefficients and standard errors between experimental and predicted quantities. Intermolecular interactions between anisole and alkanols have been studied based on the computed excess thermodynamic quantities.     

Excess molar enthalpies of formamide + some alkan-1-ols (C1-C6) and their correlations at 298.15 K

Excess molar enthalpies, H^E for the binary systems formamide+methanol, + ethanol, + propan-1-ol, + butan-1-ol, + pentan-1-ol, and + hexan-1-ol have been measured at 298.15 K and atmospheric pressure with a Paar 1455 solution calorimeter. All the system present endothermic events and showed maximum positive H^E values around 0.40-0.50 mole fraction of formamide. The H^E values increases in the order: methanol<ethanol<propan-1-ol<butan-1-ol<pentan-1-ol<hexan-1-ol. Experimental showed insolubility of hexan-1-ol in formamide around x≅0.5 mole fraction of formamide. The excess enthalpies of the above mentioned binary systems, were used to discuss interaction between the alkan-1-ols and formamide molecules. The results are interpreted to gain insight into the changes in molecular association equilibria and structural effects in these systems through O···HO hydrogen bonding. The experimental data have been correlated using Redlich-Kister polynomials. In this research work, the thermodynamics models were also tested: NRTL, Wilson models and their parameters were calculated. The correlation of excess enthalpy data in the systems using NRTL model provides good results.