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.     

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.     

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.     

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.     

Excess Thermodynamic Properties of Binary Liquid Mixtures Containing N,N -Dimethylacetamide with Some Alkan-1-Ols (C 1 -C 6 ) At 298.15 K

Excess molar enthalpies, $ H_m^E $ of N , N -dimethylacetamide + methanol, + ethanol, + propan-1-ol, + butan-1-ol, + pentan-1-ol, and + hexane-1-ol have been determined at 298.15 K and atmospheric pressure using a Parr 1455 solution calorimeter. While the excess molar enthalpies are negative for methanol and ethanol mixtures, those for propan-1-ol, butan-1-o1, pentane-1-ol, and hexan-1-ol mixtures are positive over the entire range of composition of N , N -dimethylacetamide. The $ H_m^E $ at around x , 0.5 follow the order: methanol<ethanol<propan-1-ol<butan-1-ol<pentan-1-ol<hexan-1-ol. The results are explained in terms of the self-association exhibited by the alkan-1-ols and the formation of aggregates between unlike molecules through OHO hydrogen bonding. The experimental results for mixtures are well represented by the Redlich - Kister equation.     

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.     

Aromatic substitution. The effect of alcoholic solvents on the reaction of phenyltriethyltin with mercury (II) salts

Second-order rate constants are reported for the cleavage of the phenyltin bond of phenyltriethyltin by mercury(II) salts in ethanol. propan-1-ol, propan2-ol and butan-1-ol. It is shown that the reactivity order for the mercury(II) salts is HgI₃^? << HgI₂ < HgCl₂. Activation parameters are reported, and on the basis of the low values of activation enthalpies the presence of an intermediate π-complex is suggested for the reactions.     

Volumetric Properties of (Difurylmethane + Alkan-1-ol) Binary Mixtures at 298.15 K

Densities (ρ)of the binary systems of {difurylmethane + (ethanol or propan-1-ol or butan-1-ol or pentan-1-ol or hexan-1-ol)} have been measured with an Anton Paar DMA 4500 vibrating-tube densimeter over the entire composition range at 298.15,K and atmospheric pressure. Excess molar volumes (V _m ^E ) of each binary system were determined and correlated by the Redlich-Kister equation. Limiting (V _i ^E,∞) and excess partial molar volumes (V _i ^E ) of components of each binary system have been calculated to provide insight into the intermolecular interactions present and the packing efficiencies. The results have been discussed in terms of specific intermolecular interactions, dispersive forces and structural effects.     

Study of Densities, Viscosities and Ultrasonic Speeds of Binary Mixtures Containing 1,2-Dimethoxyethane and an Alkan-l-ol at 298.15 K

The viscosity deviation (Δη), the excess molar volume (V ^E) and the ultrasonic speed (u) have been investigated from viscosity (η) and density (ρ ) measurements of binary liquid mixtures of 1,2-dimethyoxyethane with methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, hexan-1-ol or octan-1-ol over the entire range of composition at 298.15 K. The excess volumes are negative over the entire range of composition for all of the mixtures with the exception of hexan-1-ol and octan-1-ol. The excess isentropic compressibilities (K _S ^E) and viscosity deviations are negative for all of the mixtures. The magnitudes of the negative values of V ^E decrease with the number of carbon atoms of the alkan-1-ol. The trend of increasing K _S ^E values with the chain length of the alkanol is similar to that observed in the case of V ^E. Graphs of V ^E, Δ η, K _S ^E, Δ u, L _f ^E and Z ^E against composition are presented as a basis for a qualitative discussion of the results.     

Interaction of 2,2,6,6-tetramethylpiperidine-1-oxyl chloritewith alcohols

The kinetics of the oxidation of a series of alcohols (viz., ethanol, propan-2-ol, butan-1-ol, butan-2-ol, heptan-4-ol, decan-2-ol, propan-1,3-diol, butan-2,3-diol, cyclohexanol, benzyl alcohol, and borneol) with the oxoammonium salt 2,2,6,6-tetramethylpiperidine-1-oxyl chlorite in acetonitrile was studied by spectrophotometry. The products of oxidation of primary alcohols are the corresponding aldehydes and carboxylic acids, and the products of oxidation of secondary alcohols are ketones. The reaction rate is described by the second order equation. The rate constants and activation parameters were determined. The rate constant as a function of the alcohol nature is described by the one-parameter Taft equation.     

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.     

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.     

Effect of Temperature on the Volumetric Properties of [Difurylmethane+(C<Subscript>2</Subscript>–C<Subscript>6</Subscript>) Alkan-1-ol] Binary Systems: Analyses of New and Literature Density Data in the Temperature Range 288.15–308.15 K

Densities, ρ, of the binary systems {difurylmethane + (ethanol or propan-1-ol or butan-1-ol or pentan-1-ol or hexan-1-ol)} have been measured with an Anton Paar DMA 4500 vibrating-tube densimeter over the entire composition range at 288.15 and 308.15 K and atmospheric pressure. The measured and literature densities of [difurylmethane + n-alkanol] binary systems have been used to check the validity of the relationship describing the dependence of density on composition. This relation is useful for obtaining interpolated ρ values corresponding to the experimental data. Excess molar volumes (V _m^E) of each mixture, limiting (V _m,i ^E,∞) and excess partial (V _m,i ^E) molar volumes and the limiting partial molar expansion (E _p,i ^∞) of both components of each binary system have been examined to provide insight into the temperature variations of the intermolecular interactions and molecular packing efficiencies. The results have been discussed in terms of specific intermolecular interactions and structural effects.     

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.     

Isentropic Compressibility Changes of Mixing for 1,3-Dioxolane or 1,4-Dioxane + Water + Propanol Ternary Mixtures

Speed of sound data, u_ijk, of 1,3-dioxolane or 1,4-dioxane(i) + water(j) + propan-1-ol or propan-2-ol(k) ternary mixtures and their sub-binary mixtures, u_ij, of 1,3-dioxolane or 1,4-dioxane(i) + water or propan-1-ol or propan-2-ol(j) and water(i) + propan-1-ol or propan-2-ol(j) mixtures have been measured over the entire composition range at 308.15 K. Isentropic compressibility changes of mixing, (κ_s^E)_ij and (κ_s^E) _ijk, for the binary and ternary mixtures have been determined by employing the observed speeds of sound data and densities (calculated from their molar excess volumes data). The (κ_s^E) _ij and (κ_s^E) _ijk values have also been predicated by the graph theoretical approach and the Flory theory. It has been observed that (κ_s^E) _ij and (κ_s^E) _ijk predicted by the graph theoretical approach compare well with their corresponding experimental values.     

Excess Molar Enthalpies of Monoethanolamine (MEA) + Primary Alkan-1-ols (C3–C6) and their Fitting with Wilson,NRTL and UNIQUAC Models at 298.15 K

Journal of Solution Chemistry - Excess molar enthalpies, $${H}_{\text{m}}^{\text{E}}$$ of binary mixtures of monoethanolamine (MEA) with propan-1-ol, butan-1-ol, pentan-1-ol and hexan-1-ol were...     

Ultrasonic Studies in Binary Mixtures of 1-2-Dibromoethane with Alcohols at 303.15 K

Abstract

Isentropic compressibility data, K_S of 1,2-Dibromoethane + Propan-1-ol, + butan-1-ol, + pentan-1-ol, hexan-1-ol, heptan-1-ol and octan-1-ol at 303.15 K are reported. Deviations in isentropic compressibility, K_S values are found to be negative for mixtures of 1,2-dibromoethane with propan-1-ol over the entire range of composition and while in butan-1-ol the δK_S values are negative at lower molefractions and positive at higher molefractions. Therefore as the chain length increases it is showing the positive deviations. The data are interpreted in terms of specific interactions between the components.     

Enthalpies and entropies of vaporization of propan-2-ol-2-methylpropan-1-ol solutions

P-T-x dependences are measured for the solutions of a propan-2-ol-2-methylpropan-1-ol binary system and the enthalpies and entropies of vaporization are determined. Dimerization in propan-2-ol and 2-methylpropan-1-ol is rationalized and the contribution from energy introduced by isostructural methyl groups to the enthalpy of vaporization is determined. Structural and energy analyses of solutions with networks of specific interactions are performed. The formation of heterodimers in solutions and vapors with reduced hydrogen bond energies and specific interactions with the 2s ²(C) unshared electron pairs of the carbon atoms of terminal methyl groups in ethyl and propyl fragments of propan-2-ol and 2-methylpropan-1-ol, respectively, is substantiated. The hydrogen bond energy of heterodimers is estimated.