Thermophysical properties of binary mixtures (dimethyl carbonate + ketones) at T = (303.15, 308.15 and 313.15) K

The densities ρ, viscosities η, and refractive indices n_D of binary mixtures of dimethyl carbonate (DMC) with acetophenone, cyclopentanone, cyclohexanone, and 3-pentanone have been measured over the entire range of composition at the temperatures 303.15, 308.15 and 313.15 K and at atmospheric pressure. The density values were used to calculate excess molar volumes V^E, and other excess functions of interest such as deviations in viscosity Δη, excess Gibb's free energies of activation of viscous flow ΔG^E and deviations in molar refraction ΔR. The measured viscosities were compared with those predicted using the Grunberg-Nissan, Eyring-Margules, Soliman-Marshall, and McAllister four body models. Furthermore the refractive indices data have been correlated using Lorentz-Lorentz, Weiner, Newton, Gladstone-Dale, Eykman, and Eyring-John equations and a satisfactory agreement was found for all the binary systems studied in the present work.     

Thermophysical and thermoacoustical properties of acetophenone with ethyl butyrate at temperatures of 303.15, 313.15, and 323.15 K

Densities, viscosities, and ultrasonic velocities of the binary mixtures of acetophenone with ethyl butyrate were measured over the entire mole fractions at 303.15, 313.15, and 323.15 K. From these experimental results, excess molar volume V ^E , viscosity deviation Δη, deviations in isentropic compressibility Δκ _s , excess intermolecular free length ΔL _f , and excess Gibbs free energy ΔG* ^E were calculated. The viscosity values were fit to the models of Krishnan–Laddha and McAllister. The thermophysical properties under study were fit to the Jouyban–Acree model. The excess values were correlated using Redlich–Kister polynomial equation to obtain their coefficients and standard deviations. It was found that in all cases, the data obtained fitted with the values correlated by the corresponding models very well. The results are interpreted in terms of molecular interactions occurring in the solution.     

Volumetric properties and viscosities of the 2-pyrrolidone + 1,2-propanediol + water ternary system and its binary constituents at T = 313.15 K

Densities and viscosities of ternary mixtures of 2-pyrrolidone + 1,2-propanediol + water and corresponding binary mixtures of 1,2-propanediol + water, 2-pyrrolidone + water and 2-pyrrolidone + 1,2-propanediol have been measured over the whole composition range at 313.15 K. From the obtained data, the excess molar volumes (V^E), the deviations in viscosity (Δη) and the excess Gibbs free energy of activation (ΔG^?E) have been calculated. The V^E, Δη and ΔG^?E results were correlated and fitted by the Redlich–Kister equation for binary mixtures and by the Cibulka equation for ternary mixtures, as a function of mole fraction. Several predictive empirical relations were applied to predict the excess molar volumes of ternary mixtures from the binary mixing data.     

Excess molar volumes and viscosities for binary mixtures of alkoxypropanols with 1-alkanols at 298.15 K

The excess molar volumes (V_m^E) and viscosities (η) for binary mixtures of dipropylene glycol tert-butyl ether with methanol, 1-propanol, 1-pentanol, and 1-heptanol and viscosities of dipropylene glycol monomethyl ether and dipropylene glycol monobutyl ether with methanol, 1-pentanol, and 1-heptanol have been reported at 298.15 K. The V_m^E are negative for the mixtures investigated. Sign and magnitude of V_m^E and viscosity deviations were used to analyze the mixing behavior of the components.     

Studies of partial molar volumes of alkylamine in non-electrolyte solvents II. Alkyl amines in chloroalkanes at 303.15 and 313.15 K

Apparent molar volumes V_?,B of n-propylamine, n-butylamine, di-n-propylamine, di-n-butylamine, tri-n-propylamine, and tri-n-butylamine in tetrachloromethane and trichloromethane at 303.15 and 313.15 K have been calculated from the densities ρ determined with high precision vibrating tube densimeter. From these data limiting partial molar volumes V¯_B^∞ and limiting excess partial molar volumes V¯_B^E,∞ were estimated. The results are analysed and interpreted in terms of solute–solvent interactions and structural effects of the molecules. An attempt to find a measure of the contribution of the specific interactions to the partial molar volumes of primary, secondary and tertiary amines in tetra- and tri-chloromethane was made using Terasawa model, scaled particle theory (SPT) and hard sphere theory (HST).     

Densities, speeds of sound and viscosities of binary liquid mixtures of octan-2-ol with benzene and halobenzenes at 298.15 and 303.15 K

Densities ρ, speeds of sound u, viscosities η and refractive indices n_D of binary mixtures of octan-2-ol with benzene, chlorobenzene and bromobenzene have been measured over the entire range of composition at 298.15 and 303.15 K and atmospheric pressure. From the experimental data, excess molar volumes V^E, isentropic compressibilities κ_S, excess isentropic compressibilities κ_S^E, and deviations of speeds of sound u^D, have been calculated at 298.15 and 303.15 K. These excess functions have been fitted to the Redlich-Kister polynomial equation. The viscosity data have been correlated using Kendall-Monroe, Grunberg-Nissan, Tamura-Kurata, Hind-Mclaughlin Ubbelohde and Katti-Chaudhary viscosity models, and McAllister's three-body interaction model at different temperatures.     

Acoustical and excess properties of {1-hexanol + n-hexane, or n-octane, or n-decane} at (298.15, 303.15, and 308.15) K

Densities (ρ) and speeds of sound (u) for the binary mixtures of 1-hexanol with n-hexane, n-octane and n-decane have been measured over the entire composition range at 298.15, 303.15 and 308.15 K. The dynamic viscosities (η) for these systems have been measured at 298.15 K. From experimental data, excess molar volumes (V_m^E), molar isentropic compressibility (K_s,m), excess molar isentropic compressibility (K_s,m^E), deviation in speed of sound (u^D) from their ideal values (u^id) in an ideal mixture, and excess free volumes (V_f^E) have been calculated. The excess functions have also been correlated with the Redlich–Kister polynomial equation. The viscosity data have been analysed in terms of some semi-empirical equations. The theoretical values of speed of sound (u) and isentropic compressibility (κ_S) have also been estimated using the Prigogine–Flory–Patterson (PFP) theory with the van der Waals (vdW) potential energy model and the results have been compared with experimental values. The effect of chain-length of n-alkanes as well as the temperature on the excess properties has also been studied.     

RETRACTED ARTICLE: Density,viscosity and speed of sound of benzaldehyde with benzene at 303.15, 308.15, and 313.15 K

The values of density, viscosity and speed of sound for the binary liquid mixture of Benzaldehyde with Benzene were measured over the entire range of composition at 303.15, 308.15, and 313.15 K. These values are used to calculate the excess molar volume (V ^E), deviation in viscosity (Δη), deviation in speed of sound (ΔU), deviation in isentropic compressibility (Δβ _s ), excess internal pressure (Δπ), excess intermolecular free length (ΔL _f ), excess free volume (V _E ^f ) and excess acoustic impedance (ΔZ). McAllister’s three-body interaction model is used for correlating Kinematic Viscosity of binary mixtures. The excess values were correlated using the Redlich–Kister polynomial equation to obtain their coefficients and standard deviations. The thermophysical properties (density, viscosity, and speed of sound) under the study were fit to the Jouyban–Acree model.     

Ultrasonic velocity, density, viscosity and their excess parameters of the binary mixtures of tetrahydrofuran with methanol and o-cresol at varying temperatures

The ultrasonic velocity, density and viscosity of binary mixtures of tetrahydrofuran (THF) with methanol and o-cresol were measured at 293, 303 and 313 K over the entire range of composition. Using these experimental data, various thermo-acoustic parameters such as deviation in isentropic compressibility Δκ_s, excess molar volume , viscosity deviation Δη and excess Gibb’s free energy of activation for viscous flow ΔG^∗E have been calculated and fitted to Redlich-Kister polynomial equation. The deviation/excess parameter were plotted against the mole fraction of THF over the whole composition range. The observed negative and positive values of deviation/excess thermo-acoustic parameters were explained on the basis of the intermolecular interactions present in these mixtures. Since methanol is less acidic than o-cresol, the removal of proton from methanol is less likely than the removal of proton from o-cresol which is more acidic than methanol. Hence the intermolecular interaction in the mixture of THF with o-cresol is found to be stronger than mixture of THF with methanol, which is reflected from the observed positive and negative values of excess thermo-acoustic parameters. Thus it may be concluded that THF + o-cresol mixture exhibits strong intermolecular interaction. However, dispersive forces are responsible for THF + methanol mixture due to weak interaction. Further, Nomoto, Junjie, CFT and Flory’s theory were applied for evaluating the ultrasonic velocity theoretically. The theoretical evaluation of ultrasonic velocity based on molecular models in liquid mixtures has been used to correlate with the experimental findings and to know the thermodynamics of the mixtures. The comparison of theoretical and experimental results provides better understanding about the validity of the various thermodynamic, empirical, semi empirical and statistical theories.     

Excess molar volumes,viscosity deviations,excess isentropic compressibilities and deviations in relative permittivities of (alkyl acetates (methyl,ethyl, butyl and isoamyl) + n-hexane, + benzene, + toluene, + (o-, m-, p-) xylenes, + (chloro-, bromo-, nitro-) benzene at temperatures from 298.15 to 313.15 K

The experimental densities (ρ), dynamic viscosities (η), speeds of sound (υ) and relative permittivities (ε_r) of thirty six binary mixtures of esters (methyl acetate, ethyl acetate, butyl acetate and isoamyl acetate) + organic solvents (n-hexane, benzene, toluene, o-, m-, p- xylenes), + halogenated benzene (chloro-, bromobenzene), + nitrobenzene have been measured over the complete composition range at atmospheric pressure and temperatures (298.15 to 313.15 K). The excess molar volumes, V_m^E, excess isentropic compressibilities, κ_s^E, deviations in relative permittivities, δε_r have been calculated and fitted to Redlisch–Kister type equation. The dynamic and kinematic viscosities have been correlated through Grunberg–Nissan and MacAllister equations. The qualitative analysis of various functions revealed that i.) esters lose their dipolar association in presence of inert and unlike n-hexane, ii.) specific but weaker n…π type interactions predominate in binary mixtures of esters + aromatic organic solvents and iii.) weak electron donor–acceptor complexes predominate in the mixtures of esters with halogenated and nitrated benzene.     

Analysis of average primary gamma-transition intensities and cross sections of the113Cd(n, γ) reaction

A combined analysis of the available data on the primaryγ-ray intensities from the¹¹³Cd(n, γ) reaction atE _n=1.9 and 24.3 keV neutron energies together with the data on¹¹³Cd neutron capture cross sections in theE _n=3–200 keV energy region was carried out. The neutron strength functions were determined asS _n0=(0.260±0.073) 10^?4 and S_n1=(5.06±0.67) 10^?4. No spin-orbit splitting of thep-wave neutron strength function was found. The energy dependence of theE 1 radiative strength function {ie147-01} was fitted by the Kadmenski-Furman model somewhat better than by a standard Lorentzian. TheM 1 giant resonance parameters were obtained as E _G ^{M 1} =8.8±1.6 MeV and Γ _G ^{M 1} = 4.7±2.6 MeV. The neutron capture cross section of¹¹³Cd from its isomeric state ({ie147-02}=11/2^?, E ₁ ^m =263.7 keV) was calculated.     

Image potential eigenstates and resonances on the (110) surfaces of noble metals: Energies and lifetimes

The energies and lifetimes of the image potential resonances at the ? point on the Cu(110), Ag(110), and Au(110) surfaces are studied, and the energies of the image potential states on the Pd(110) surface are analyzed. It is shown that every quantum number n corresponds to a pair of image potential states (resonances) n ⁺ and n ^? at the ? point. The average energy of a pair of eigenstates (resonances) at n ≥ 2 is well described by the formula ē _n = (E _n+ + E _n?) = E ₀ ? (0.85 eV)/(n + δ)², where δ is the quantum defect, E ₀ = (1/2m _e )(?π/a)², and a is the lattice parameter. The splitting energy of a pair of eigenstates (resonances) obeys the law ΔE _n = E _n+ — E _n? ∝ n ^?3. The lifetimes τ _n± of image potential resonances are proportional to n ³.     

Molecular interactions in ternary organic liquid mixtures

Excess volumes (V₁₂₃^E) of five ternary mixtures were measured at 303.15 K. The mixtures include acetophenone and 1-propanol as common components. The non-common components chosen in the present investigation are benzene, toluene, chlorobenzene, bromobenzene and nitrobenzene. The measured excess volume data are negative over the entire composition range in the mixtures containing chlorobenzene, bromobenzene and nitrobenzene. On the other hand, the quantity exhibits an inversion in sign in the remaining two mixtures. The experimental results were compared with those predicted by empirical relations.     

A measurement of the ratio GE/GE of the proton form factors at very low momentum transfer

The ratioμG _EG_M of the proton form factors was determined by measuring the electron scattering cross section of the proton relative to that of¹²C. Data were taken atq ²=0.09, 0.16, 0.25, and 0.36 fm^?2, yielding a weighted mean ofμG _E/G_M=1.01±0.03.     

Fragmentation processes of vanadium and niobium oxide clusters sputtered by ion bombardment

The mass distribution of emitted V _n O _m ^? and Nb _n O _m ^? clusters and their unimolecular decay by all stoichiometrically possible fragmentation channels, which takes place under the sputtering of niobium and vanadium surfaces and blowing by oxygen, are studied. It is shown that the formation, excitation, and unimolecular fragmentation of V _n O _m ^? and Nb _n O _m ^? clusters can be described by a statistical recombination mechanism. Clusters are formed over the target surfaces as a result of binary collisions of independently sputtered ions, atoms, and molecules.     

A tem study of the crystallization behavior in amorphous vacuum condensed Er—Cu thin films

The isothermal crystallization of amorphous, vacuum condensed Er_0.6Cu_0.4 thin films was investigated in situ by transmission electron microscopy. Heterogeneous nucleation of ErCu crystallites was observed to occur on the thin rare-earth oxide layer which is inevitably formed on the external surface of the thin film exposed to the ambient atmosphere. The crystalline particles exhibited preferential growth in the direction parallel to the surface of the film. The crystallization process is interface controlled and characterized by a constant nucleation and constant growth rate. The kinetics of transformation were anslyzed in terms of Avrami's equation. The kinetic exponent n in Avrami's equation is equal to 2.9 in good agreement with the theoretical value for two-dimensional, interface-controlled growth. The experimental date allowed to derive the values of ΔE = 581 kJ.mole^?1 for the overall activation energy of the crystallization reaction, Δ_cr = 151 kJ.mole^?1 for the energy of critical nucleus formation and ΔE_m = 143 kJ.mole^?1 for the activation energy of atomic motion.     

The thermodynamics of solid solutions of argon and methane

The primary concern of this paper is with the estimation of the excess Gibbs energy G^E,S for solid solutions of two molecularly simple components which are completely miscible in the solid state. The method depends on combining information on the excess thermodynamic functions of liquid mixtures of the two components with a knowledge of the liquidus and solidus lines on the temperature-composition phase diagram. It is applied to the particular case of argon-methane. For this system, unit cell sizes and some heat of fusion measurements are also available, from which V^E,S and H^E,S have been calculated.A solid solution of argon and methane departs much more from ideality than does a liquid mixture of the same composition at the same temperature, the ratio r, = G^E,S/G^E,L, being about 3. Moreover, the concentration dependence of G^E,S is less symmetrical than that of G^E,L, and the ratio r increases markedly with increasing argon mole fraction. A dilute solution of methane (which has the larger molecules) in argon has a larger G^E,S than the corresponding dilute solution of argon in methane.For a solid solution at 71 K with an argon mole fraction of 0.60, H^E,S is ≈4801 Jmol^?1. This gives TS^E,S ≈ 220 J mol^?1, which is about the same as G^E,S. The solid solutions cannot therefore be regarded as even approximating to regular solutions.From the calculated G^E,S results, it is predicted that the face-centred cubic solid solutions of argon and methane should separate into two phases on cooling. The calculated coordinates of the upper critical solution point are T = 67 K and an argon mole fraction of 0.63, in reasonable agreement with the experimental values of 63 K and 0.65 respectively.     

Densities, excess molar volumes, and viscosities of the binary and ternary mixtures of {diethylcarbonate (1) + p-chloroacetophenone (2) + 1-hexanol (3)} at 303.15 K for the liquid region and at ambient pressure

Densities ρ, dynamic viscosities η, of the ternary mixture (diethylcarbonate + p-chloroacetophenone + 1-hexanol) and the involved binary mixtures (diethylcarbonate + p-chloroacetophenone), (diethylcarbonate + 1-hexanol), and (p-chloroacetophenone + 1-hexanol) have been measured over the whole composition range at 303.15 K for the liquid region and at ambient pressure. The data obtained are used to calculate excess molar volumes V_m^E, excess partial molar volumes V¯_m,i^E, limiting excess partial molar volumes V¯_m,i^E,∞, and viscosity deviations Δη, of the binary and ternary mixtures. The data of excess molar volumes of the binary systems were fitted to the Redlich–Kister equation while for the ternary system the Cibulka equation was used. The McAllister's four body, and Kalidas and Laddha interaction models are used to correlate the kinematic viscosities of binary and ternary mixtures, respectively, to determine the fitting parameters and the standard deviations. The experimental data of the constitute binaries and ternary are analyzed to discuss the nature and strength of intermolecular interactions in these mixtures.     

Thermodynamic investigations of ternary o-toluidine + tetrahydropyran + N,N-dimethylformamide mixture and its binaries at 298.15, 303.15 and 308.15 K

The densities ρ, speed of sound u, data of o-toluidine (i) + tetrahydropyran (j) + N,N-dimethylformamide (k) and its {tetrahydropyran (j) + N,N-dimethylformamide (k); o-toluidine (i) + N,N-dimethylformamide (k)} binaries have been measured as a function of composition at 298.15, 303.15 and 308.15 K. The excess molar enthalpies, H^E data of same set of binary mixtures have also been measured over entire composition at 308.15 K. The densities and speeds of sound data of binary and ternary mixtures have been utilized to determine their excess molar volumes, V^E and excess isentropic compressibilities, κ_S^E. The observed thermodynamic properties of binary and ternary mixtures have been analyzed in terms of Graph theory. It has been observed that Graph theory correctly predicts the sign as well as magnitude of thermodynamic properties.