Notion of viscosity Arrhenius temperature for N,N-dimethylacetamide with N,N-dimethylformamide binary mixtures and its pure components

Excess properties calculated from the experimental values of densities and viscosities have been presented in the previous work. These experimental values can also lead us to test different correlation equations as well as their corresponding relative functions. Inspection of the Arrhenius activation energy Ea and the enthalpy of activation of viscous flow ΔH* found very close values, here we can define partial molar activation energy Ea₁ and Ea₂ for N,N-dimethylacetamide and methanol respectively along with their individual contribution separately. Correlation between the two Arrhenius parameters of viscosity in all compositions shows existence of distinct behaviours separated by particular mole fractions of N,N-dimethylacetamide. In addition, the correlation between Arrhenius parameters reveals interesting Arrhenius temperature which is closely related to the vaporisation temperature in the liquid vapour equilibrium and the limiting corresponding partial molar properties that can permit us to estimate the boiling points of the pure components.     

A novel approach to discuss the viscosity Arrhenius behaviour and to derive the partial molar properties in binary mixtures of N,N-dimethylacetamide with 2-methoxyethanol in the temperature interval (from 298.15 to 318.15) K

Calculation of excess properties in N,N-dimethylacetamide + 2-methoxyethanol binary mixtures at (298.15, 308.15 and 318.15) K from experimental density, viscosity and sound velocity values were presented in previous work. Applications of these experimental values to test different correlation equations as well as their corresponding relative functions were also reported. Considering the quasi-equality between the Arrhenius activation energy Ea and the enthalpy of activation of viscous flow ΔH*, here we can define partial molar activation energy Ea₁ and Ea₂ for N,N-dimethylacetamide and 2-methoxyethanol, respectively, along with their individual contribution separately. Correlation between Arrhenius parameters reveals interesting Arrhenius temperature with a comparison to the vaporisation temperature in the liquid vapour equilibrium, and the limiting corresponding partial molar properties that can permit us to estimate the boiling points of the pure components.     

Estimation of the normal boiling points of water and 1,2-dimethoxyethane through the viscosity–temperature dependence in the corresponding binary mixtures

Excess quantities calculated from literature values of experimental density and viscosity in 1,2-dimethoxyethane + water binary systems (from 303.15 to 323.15 K) can lead us to test different correlation equations as well as their corresponding derivative properties. Inspection of the Arrhenius activation energy (Ea) and the enthalpy of activation of viscous flow (ΔH*) shows very close values; here, we can define partial molar activation energies Ea₁ and Ea₂ for 1,2-dimethoxyethane and water, respectively, along with their individual contribution separately. Correlation between the two Arrhenius parameters of viscosity in all compositions shows existence of main distinct interaction behaviours delimited by particular mole fractions in 1,2-dimethoxyethane. Moreover, we add that correlation between Arrhenius parameters reveals interesting Arrhenius temperature which is closely related to the vapourisation temperature in the liquid vapour equilibrium, and the limiting corresponding partial molar properties can permit us to estimate the boiling points of the pure components.     

A partial derivatives approach for estimation of the viscosity Arrhenius temperature in N,N-dimethylformamide + 1,4-dioxane binary fluid mixtures at temperatures from 298.15 K to 318.15 K

Excess properties calculated from the literature values of experimental density and viscosity in N,N-dimethylformamide (DMF) + 1,4-dioxane (DO) fluid binary mixtures (from 303.15 to 318.15) K can lead us to test the different correlation equations as well as their corresponding relative functions. Inspection of the Arrhenius activation energy Ea and the enthalpy of activation of viscous flow ?H* shows very close values; here we can define partial molar activation energy Ea₁ and Ea₂ for DMF and DO, respectively, along with their individual contribution separately. Correlation between the two Arrhenius parameters of viscosity in all compositions shows the existence of the primary distinct behaviours separated by particular mole fractions in DMF. In addition, we add that the correlation between Arrhenius parameters reveals interesting Arrhenius temperature (T_A), which is closely related to the vaporisation temperature in the liquid–vapour equilibrium; moreover, the limiting corresponding partial molar properties allow us to estimate the boiling points of the pure components.     

Estimation of boiling points by investigations of viscosity Arrhenius behaviours in Methyl Benzoate + n-Hexane binary liquid systems at atmospheric pressure

Calculation of excess properties in methyl benzoate + n-Hexane binary liquid mixtures at (303.15, 308.15 and 313.15) K from experimental viscosity and density values was presented in earlier work. Investigations of these experimental values to test correlation quality of different equations as well as their corresponding relative functions were also reported. Considering the quasi-equality between the enthalpy of activation of viscous flow ΔH* and the viscosity Arrhenius activation energy Ea, here we can define partial molar activation energy Ea₁ and Ea₂ for methyl benzoate with n-Hexane, respectively, along with their individual contribution separately. Correlation between Arrhenius parameters brings to light interesting Arrhenius temperature with a comparison to the temperature of vaporisation in the liquid vapour equilibrium, and the limiting corresponding partial molar properties that can permit us to predict value of the boiling points of the pure components. New empirical equations for estimating the boiling temperature are proposed.     

Viscosity Arrhenius activation energy and derived partial molar properties in N,N-Dimethylacetamide + water binary mixtures at temperatures from 298.15 to 318.15 K

Calculation of excess properties in N,N-dimethylacetamide + water binary mixtures at (298.15, 308.15 and 318.15) K from experimental density, viscosity and sound velocity values were presented in previous work. Applications of these experimental values to test different correlation equations as well as their corresponding relative functions were also reported. Considering the quasi-equality between the Arrhenius activation energy Ea and the enthalpy of activation of viscous flow ΔH*, here we can define partial molar activation energy Ea ₁ and Ea ₂ for N,N-dimethylacetamide and water respectively along with their individual contribution separately. Correlation between the two Arrhenius parameters of viscosity in all the domains of composition shows the existence of two main distinct behaviours separated by a stabilised structure in a short range of mole fraction in N,N-dimethylacetamide from 0.2 to 0.3. We add that correlation reveals interesting Arrhenius temperature which is closely related to the vapourisation temperature in the liquid vapour equilibrium.     

On the viscosity Arrhenius temperature for methanol + N,N-dimethylformamide binary mixtures over the temperature range from 303.15 to 323.15 K

Excess properties calculated from literature values of experimental density and viscosity in N,N-dimethylformamide (DMF) + methanol (Met) binary mixtures (from 303.15 to 323.15 K) can lead us to test different correlation equations as well as their corresponding derivative properties. Inspection of the Arrhenius activation energy (E_a) and the enthalpy (ΔH*) of activation of viscous flow shows very close values; here, we can define partial molar activation energies E_a1 and E_a2 for N,N-DMF and Met, respectively, along with their individual contribution separately. Correlation between the two Arrhenius parameters of viscosity in all compositions shows existence of main distinct interaction behaviours delimited by particular mole fractions in N,N-DMF. In addition, we add that correlation between Arrhenius parameters reveals interesting Arrhenius temperature that is closely related to the vaporisation temperature in the liquid vapour equilibrium, and the limiting corresponding partial molar properties can permit us to estimate the boiling points of the pure components.     

Viscosity Arrhenius activation energy and derived partial molar properties in of N,N-dimethylacetamide + 2-ethoxyethanol binary mixtures at temperatures from 298.15 K to 318.15 K.

Calculation of excess properties in N,N-dimethylacetamide + 2-ethoxyethanol binary mixtures at (298.15, 308.15 and 318.15) K from experimental density, viscosity and sound velocity values were presented in previous work. Applications of these experimental values to test different correlation equations as well as their corresponding relative functions were also reported. Considering the quasi-equality between the Arrhenius activation energy Ea and the enthalpy of activation of viscous flow ?H*, here we can define partial molar activation energy Ea1 and Ea2 for N,N-dimethylacetamide and 2-ethoxyethanol, respectively, along with their individual contribution separately. Correlation between the two Arrhenius parameters of viscosity in all the domains of composition shows the existence of two main distinct behaviours separated by a stabilised structure in a short range of mole fraction in N,N-dimethylacetamide from 0.14 to 0.45. We add that correlation reveals interesting Arrhenius temperature, which is closely related to the vaporisation temperature in the liquid vapour equilibrium.     

Viscosity of Aqueous Solutions of Formamide,N-Methylformamide and N,N-Dimethylformamide

Abstract

Viscosities of aqueous solutions of formamide, N-methylformamide and N,N-dimethylformamide have been measured at temperatures 303.15, 308.15, 313.15, 318.15 and 323.15 K. For formamide + water system the viscosity increases exponentially with respect to the mole fraction of formamide. In contrast, N-methylformamide+water and N,N-dimethylformamide+water systems exhibit maxima in water-rich region, the maxima of the latter being higher and sharper than those of the former system. The excess viscosities of formamide+water system are positive at 323.15 K, which turn to negative values at 303.15 K, the magnitude of the values being very small irrespective of their sign. On the other hand, N-methylformamide+water and N,N-dimethylformaide+water systems show large positive excess viscosities for the whole range of composition. The viscosities and excess viscosities for the system formamide+water have been explained by assuming some complex formation between the components with the simultaneous disruption of water structures. For N-methylformamide+water and N,N-dimethylformamide+water systems, it has been assumed that cluster-like structure of water is formed around methyl group(s) attached to N-atom of the amides, which influences the viscosity behaviour of these systems strongly.     

Effect of Temperature and Composition on the Transport and Thermodynamic Properties of Binary Mixtures of Ionic Liquid <Emphasis Type="Italic">N</Emphasis>-Butyl-<Emphasis Type="Italic">N</Emphasis>-methylpyrrolidinium bis(Trifluoromethanesulfonyl)imide and Propylene Carbonate

The thermodynamic and transport proprieties have been determined for the whole concentration range of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P₁₄) and propylene carbonate (PC) binary mixtures in the temperature range 293.15–318.15 K. Strong effects of the mole fraction and temperature on these properties have been observed. The isobaric expansivities and excess properties have been evaluated. Their corresponding coefficients were positive but the excess volume had both negative and positive values. The viscosity parameter was found to be temperature-dependant and followed the Arrhenius law. The variation of activation energies for viscous flow E _a,η versus the ILs concentration exhibited a change in the medium structure. The conductivity-temperature relationship was found to have a better fitting on the Vogel-Tammann-Fulcher model than on the Arrhenius law. In addition, the variation of conductivity with the molar fraction was well described by the Casteel-Amis equation. Finally, the Walden product showed significant dependence of the conductivity on the viscosity of the medium. The results allowed good characterisation of both the ruling interactions and the medium structure.     

The reduced Redlich–Kister equations for correlating volumetric and viscometric properties of N,N-dimethylacetamide + dimethylformamide binary mixtures at temperatures from 298.15 to 318.15 K

Excess molar volumes and viscosity deviations in N,N-dimethylacetamide?+?dimethylformamide binary mixtures at 298.15, 308.15 and 318.15?K were calculated from experimental density and viscosity data presented in the previous work. Here these experimental values were used to test the applicability of the correlative reduced Redlich–Kister equation and the recently proposed Herráez equation. Their correlation ability at different temperatures, and the use of different number of parameters, is discussed for the case of limited experimental data. These relative functions are important to reduce the effect of temperature and, consequently, to reveal the effects of different types of interactions. Limiting excess partial molar volumes at infinite dilution were deduced from different methods, parameters of molar Gibbs energy of activation of viscous flow against compositions were investigated. The results of these observations have been interpreted in terms of structural effects of the solvents. ¹H-NMR studies of these mixtures are also reported.     

Complex Permittivity Spectra of Binary Pyridine–Amide Mixtures Using Time–Domain Reflectometry

Frequency spectra of the complex permittivity for pyridine–amide binary mixtures have been determined over the frequency range 10 MHz to 10 GHz, at 5, 15, 25, and 40°C, using the time–domain reflectometry method, for 11 compositions of each pyridine–amide system, e.g., formamide, N-methylformamide, and N,N-dimethylformamide. The relaxation in these systems can be described by a single relaxation time using the Debye model. The static dielectric constant, relaxation time, the corresponding excess dielectric properties, Kirkwood correlation factor, and molar activation energy of the mixtures have been determined. The excess permittivity is found to be positive in the amide-rich region and negative in the pyridine-rich region. The excess inverse relaxation time is negative, except in the pyridine-rich region. The static dielectric constants for the mixtures have been fitted with the modified Bruggeman model. The temperature-dependent relaxation times show the expected Arrhenius behavior.     

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.     

Viscosity Arrhenius Activation Energy and Derived Partial Molar Properties in 1,4-Dioxane + Water Binary Mixtures from 293.15 to 323.15 K

The knowledge and prediction of physicochemical properties of binary liquid mixtures is of great importance for understanding intermolecular interactions. Viscosities (η) have been investigated by using density (ρ) and kinematic viscosity (ν) measurements for 1,4-dioxane + water (D–W) mixtures over the entire range of mole fractions under atmospheric pressure, at 311.15, 316.15 and 320.15 K, in order to increase the studied temperatures range available from the literature and to improve the investigations. The viscosity Arrhenius activation energy of 1,4-dioxane + water mixtures was calculated from the present experimental viscosity measurements, and those presented in a previous work at only four temperatures, and for three temperatures in the present work, over the entire range of composition in the temperatures range from 293.15 to 323.15 K. Based on the partial molar activation energy from the Arrhenius equation for viscosity, interactions between water and 1,4-dioxane molecules are discussed. Comparison between some reduced Redlich–Kister functions covering the composition domain shows the existence of two distinct behaviors.     

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

Excess molar volumes, viscosity deviations, and isentropic compressibility changes in N,N-dimethylacetamide + water binary mixtures at (298.15, 308.15 and 318.15)?K were calculated from experimental density, viscosity and sound velocity results presented in previous work. Here these experimental values were used to test the applicability of the correlative reduced Redlich?CKister equation and the recently proposed Herráez equation, as well as their corresponding relative functions. Their correlation ability at different temperatures, and the use of different numbers of parameters, are discussed for the case of limited experimental data. The relative functions are important to reduce the effect of temperature and, consequently, to reveal the effects of different types of interactions. Values of the limiting excess partial molar volume at infinite dilution were deduced using different methods. Also, the activation parameters and partial molar Gibbs energy of activation of viscous flow were analyzed as functions of composition. Correlation between the two Arrhenius parameters of viscosity in all composition domains show the existence of two distinct behaviors, separated by a stabilized structure over a short range of mole fractions from (0.2?to?0.3) in N,N-dimethylacetamide. In this regard, a correlation equation recently proposed by Belda has also been applied to the present system for deriving molar volume properties, in order to assess the validity of the proposed equation,     

Reaction of iodo(trimethyl)silane with <Emphasis Type="Italic">N,N</Emphasis>-dimethyl carboxylic acid amides

The reactions of iodo(trimethyl)silane with N,N-dimethylformamide and N,N-dimethylacetamide Me₂NCOR (R = H, Me) at a molar ratio of 1: 2 involved mainly cleavage of the N-C(=O) bond with formation of up to 80% of N,N-dimethyltrimethylsilylamine Me₃SiNMe₂ and the corresponding acyl iodide RCOI. In the reaction with N,N-dimethylformamide, formyl iodide HCOI was detected for the first time by gas chromatography-mass spectrometry. The contribution of Me-N bond cleavage, leading to N-methyl-N-trimethylsilyl derivative Me(Me₃Si)NCOR and methyl iodide was considerably smaller. Another by-product was the corresponding N-methyl imide MeN(COR)₂ formed by reaction of the initial amide with acyl iodide. The primary intermediate in the reaction of iodo(trimethyl)silane with DMF and DMA is quaternary ammonium salt [Me₂(Me₃Si)N⁺COR] I⁻ which decomposes via dissociation of the N-CO and N-Me bonds.     

Volumetric and Viscometric Studies of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-Bis(salicylaldehyde)-1,3-diaminopropane Schiff Base (Salpr) in Ionic Liquid + DMF solutions

The apparent molar volumes and viscosities of N,N′-bis(salicylaldehyde)-1,3-diaminopropane Schiff base (Salpr) have been determined in ionic liquid {1-pentyl-3-methylimidazolium bromide ([PnMIm]Br)} + N,N-dimethylformamide (DMF) solutions at 298.15 K from density and viscosity measurements using a vibrating tube densimeter and übbelohde type viscometer, respectively. These data have been used to calculate standard partial molar volumes, V_f ⁰V_{\phi} ^{0}, transfer partial molar volumes, Δ_tr V ⁰, and viscosity B-coefficients of the solutions. The transfer partial molar volumes are negative, and decrease with increasing the concentration of ionic liquid for all of the investigated solutions. It found that this ionic liquid interacts strongly with the Schiff base (Salpr) and has desolvation effect on the Schiff base molecules.     

Solvent effects on the redox potential of cis-tetracarbonyl-bis-(1,3 dimethylimidazolidin-2-ylidene) chromium(0)

Polarography and cyclic voltammetry have been performed on cis-tetracarbonyl-bis-(1,3 dimethylimidazolidin-2-ylidene) chromium(0) [cis(imidine)₂Cr(CO)₄] in dichloromethane, 1,2-dichloroethane, methanol, ethanol, nitromethane, 2,2′ thiodiethanol, acetonitrile, formamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylthioformamide, acetone, propylene carbonate, N-methylpyrrolidone(2), N-methylthiopyrrolidone(2), tetramethylene sulfone, butyrolactone, N,N,N′,N′-tetramethylurea, N,N-diethylacetamide, N,N-dimethylacetamide, trimethylphosphate, dimethylsulfoxide and hexamethylene phosphoric acid triamide.A reversible oxidation to the [cis(imidine)₂Cr(CO)₄]⁺ cation has been observed in the solvents mentioned. The half-wave and 1/2(E_pa+E_pc) potentials recorded vs. bisbiphenylchromium(I)/bisbiphenylchromium(0) as a reference redox system were found to shift to more positive values with increasing electron-pair donor properties of the solvents. The polarographic and voltammetric behaviour of ferrocene and bisbiphenylchromium tetraphenyloborate has been studied in N,N-diethylacetamide, N,N-dimethylacetamide, formamide, trimethylphosphate, N,N,N′,N′-tetramethylurea and hexamethylene phosphoric acid triamide.     

Nonelectrolyte Solvation in Aqueous Dimethyl Sulfoxide—A Calorimetric and Infrared Spectroscopic Study

We report enthalpies of solution of formamide, N,N-dimethylformamide,N,N-dimethylacetamide, acetic acid, methyl acetate, and acetonitrile in water +dimethylsulfoxide mixed solvents. These, along with literature data for additional solutes,are analyzed in terms of the extended coordination model of solvation. We alsoanalyze infrared data for several of these solutes. These analyses show thatN,N-dimethylformamide and N,N-dimethylacetamide are preferentially hydrated,while the other solutes appear to be preferentially solvated by dimethylsulfoxide.In all cases, the extent of preferential solvation is relatively small. It is also foundthat the degrees of preferential solvation recovered from analyses of the enthalpydata correspond closely to those recovered from the infrared data, although thelatter refer only to the polar chromophores on the solute molecules. It is foundthat the extent to which the solutes disrupt the solvent-solvent interactions variessystematically with the area of the nonpolar surfaces of the solute molecules.