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1.
Densities, ρ, and speeds of sound, u, of systems formed by 2-methoxyethanol (2ME), 2-ethoxyethanol (2EE), 2-propoxyethanol (2PE), or 2-butoxyethanol (2BE) and 1-butanol have been measured at 293.15, 298.15 and 303.15 K and atmospheric pressure using a vibrating tube densimeter and sound analyser Anton Paar model DSA-5000. The ρ and u values were used to calculate excess molar volumes, VE, at those temperatures and deviations from the ideal behaviour of the thermal expansion coefficient, ΔP, or of the isentropic and isothermal compressibilities, ΔκS and ΔκT at 298.15 K. From the data, it is apparent that the interactional contribution to VE is more important for systems with 2ME or 2EE, while structural effects are more relevant in the 2PE or 2BE mixtures, and that dipolar interactions decrease with the size of the 2-alkoxyethanol. Several methods are applied to predict speeds of sound: free length theory (FLT), collision factor theory (CFT), and Nomoto, Junjie and Van Dael equations. CFT and Nomoto's equation provide the better predictions. Finally, 1-butanol + 2-alkoxyethanol, or + 2-(2-alkoxyethoxy)ethanol mixtures have been studied using ERAS. Poorer results were obtained for systems including 2-(2-alkoxyethoxy)ethanols, which may be due to dipolar interactions and structural effects are more important in such solutions.  相似文献   

2.
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, HE 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, VE and excess isentropic compressibilities, κSE. 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.  相似文献   

3.
Viscosities of the ternary and binary mixtures of 1-octene, Rhodorsil H68, Rhodorsil 308V750 have been measured at different temperatures between 293.15 and 353.15 K and at atmospheric pressure. Two correlations were established to predict the viscosity of all mixtures. The first is a statistical expression deduced from an experimental design. The second is based on an additivity law and the temperature effect on binary mixtures.  相似文献   

4.
Densities and viscosities of mixtures of isopropanol, isobutanol and isoamylalcohol with equimolar mixture of ethanol and N,N-dimethylacetamide have been measured at 308.15 K over the entire composition range. Deviations in viscosity, excess molar volume and excess Gibb’s free energy of activation of viscous flow have been calculated from the experimental values of densities and viscosities. Excess properties have been fitted to the Redlich-Kister type polynomial equation and the corresponding standard deviations have been calculated. The experimental data of viscosity have been used to test the applicability of empirical relations of Grunberg-Nissan, Hind-McLaughlin, Katti-Chaudhary and Heric-Brewer for the systems studied. Molecular interactions in the liquid mixtures have been investigated in the light of variation of deviation and of excess values in evaluated properties.  相似文献   

5.
Densities ρ, speeds of sound u, viscosities η and refractive indices nD 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 VE, isentropic compressibilities κS, excess isentropic compressibilities κSE, and deviations of speeds of sound uD, 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.  相似文献   

6.
The densities ρ, viscosities η, and refractive indices nD 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 VE, and other excess functions of interest such as deviations in viscosity Δη, excess Gibb's free energies of activation of viscous flow ΔGE 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.  相似文献   

7.
Densities and relative permittivities at T = (293.15, 298.15, and 303.15) K in the binary mixtures of 2-butoxyethanol with ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol have been measured as a function of composition. From the experimental data excess molar volumes and deviations in relative permittivity have been calculated over the entire composition range. Both excess molar volumes and relative permittivity deviations have been correlated using Redlich–Kister type polynomial equation by the method of least-squares for the estimation of the binary coefficients and the standard errors. The experimental and calculated quantities were used to analyze the mixing behaviour of the components.  相似文献   

8.
Densities and viscosities have been measured as a function of composition for the binary liquid mixture of diethylene glycol monomethyl ether CH3O(CH2)2O(CH2)2OH + water at T = (293.15, 303.15, 313.15, 323.15, 333.15) K under atmospheric pressure. Densities were determined using a capillary pycnometer. Viscosities were measured with Ubbelohde capillary viscometer. From the experimental data, the excess molar volumes VE, and viscosity deviations δη, and the excess energies of activation for viscous flow ΔG*E were calculated. These data have been correlated by the Redlich–Kister type equations to obtain their coefficients and standard deviations. The results suggest that molecular interaction between diethylene glycol monomethyl ether and water is strong.  相似文献   

9.
10.
Ultrasonic investigation has been carried out on six ternary systems to establish the complex formation between p-chloranil (acceptor) and six aromatic hydrocarbons (donors), namely, benzene, toluene, o-xylene, m-xylene, p-xylene and mesitylene in DMSO medium at 303.15 K and at atmospheric pressure. Studies were carried out in the concentration range of 0.002 to 0.02 M of acceptor and donor with equimolar concentration of the two components in solution. The trend in the acoustical parameters and magnitude of excess thermo acoustical parameters has been used to identify the existence of strong intermolecular interaction through charge transfer complex formation. The formation of 1:1 complex was also confirmed by UV-Visible spectroscopic method at 303.15 K in these systems. It may be pointed out that the formation constants of the charge transfer complexes determined by Benesi-Hildebrand (spectroscopic) and Kannappan (ultrasonic) methods show similar trend and well establish the influence of structural aspect of the donor aromatic compounds on the stability of charge transfer complexes.  相似文献   

11.
High-resolution core-level data from the prototypical In/Si(1 1 1) system have been acquired at 10 K. An asymmetric tail in the In 4d spectra reveals a metallic character of the low temperature Si(1 1 1)8 × 2 phase confined to the inner indium rows. The decoupling of the one-dimensional inner indium chains from any metallic environment at ∼10 K suggests a possible Luttinger liquid behavior. At room temperature essentially a broadening of the spectral features is noticed, which appears compatible with a fluctuation scenario.  相似文献   

12.
Viscometric and ultrasonic studies have been carried out in n-hexane solutions, containing equimolar concentration from 0.02 to 0.2 M of aromatic ketones and N-methylaniline (NMANI), at 303.15 K and at atmospheric pressure. The ketones studied in the present investigation are acetophenone (ACP), 4-chloroacetophenone (ClACP) and 4-methylacetophenone (MACP). The behaviour of measured ultrasonic velocity (u), density (ρ) and viscosity (η) and also the computed acoustic parameters provide strong evidence for the presence of strong solute-solute interactions in the three ternary systems. Excess molar volume and excess thermo acoustic parameters reveal the existence of hydrogen bonded complexes between the solute molecules, ketones and secondary amine. The variation of these parameters with the concentration shows that the existing interactions are influenced by the structure of components and functional groups of the components involved. An attempt has been made to confirm the formation of 1:1 complexes in these systems through UV-visible spectroscopic method at 303.15 K. The calculated values of formation constants of the charge transfer complexes both by acoustic and optical methods agree satisfactorily. The variation in the values of formation constant reveals that electron releasing substituent in the acetophenone molecule enhances the stability while electronegative substituent decreases the stability of the complex. The negative values of free energy of formation of these three complexes indicate that these complexes are thermodynamically stable.  相似文献   

13.
Densities and viscosities of glycine and l-valine have been measured at 308.15 and 318.15 K in aqueous tripotassium citrate solutions ranging from 0.2 to 0.8 mol kg− 1 of tripotassium citrate. The viscosity data have been analyzed by Jones-Dole equation. The activation parameters of viscous flow have been obtained to throw light on the mechanism of viscous flow. The values of apparent molar volume, partial molar volume at infinite dilution and relative viscosities of each amino acid in various aqueous tripotassium citrate solutions have been evaluated from the density and viscosity data. The partial molar volumes of transfer from water to aqueous tripotassium citrate solution at infinite dilution have also been calculated. Transfer volume data have been used to calculate the pair and triplet interactions. The results have been discussed in terms of solute-solute and solute-solvent interactions and the structural changes of the solutes in solutions.  相似文献   

14.
Electronic, magnetic and structural properties of atomic oxygen adsorbed in on-surface and subsurface sites at the two most densely packed iron surfaces are investigated using density functional theory combined with a thermodynamics formalism. Oxygen coverages varying from a quarter to two monolayers (MLs) are considered. At a 1/4 ML coverage, the most stable on-surface adsorption sites are the twofold long bridge sites on the (1 1 0), and the fourfold-hollow sites on the (1 0 0) surface. The presence of on-surface oxygen atoms enhances the magnetic moments of the atoms of the two topmost Fe layers. Detailed results on the surface magnetic properties, due to O incorporation, are presented as well. Subsurface adsorption is found unfavored. The most stable subsurface O, in tetrahedral positions at the (1 0 0) and octahedral ones at the (1 1 0) surface, are characterized by substantially lower binding than that in the on-surface sites. Subsurface oxygen increases the interplanar distance between the uppermost Fe layers. The preadsorbed oxygen overlayer enhances binding of subsurface O atoms, particularly for tetrahedral sites beneath the (1 1 0) surface.  相似文献   

15.
The interface between Pt and Zn-terminated ZnO(0 0 0 1) was investigated by X-ray and ultra violet photoelectron spectroscopy in order to examine electronic band alignment. An angle-resolved X-ray photoelectron spectroscopy measurement of the clean ZnO(0 0 0 1) surface has revealed a downward band bending by 0.25 eV. The results of the valence band analysis show that the work function and the valence band maximum of clean ZnO(0 0 0 1) were 4.49 eV and 2.79 eV, respectively. Platinum was then deposited in several deposition steps onto a clean ZnO(0 0 0 1) surface up to 0.6 nm in thickness. After the deposition, the binding energy of Zn 2p doublet peak was shifted towards lower value by 0.77 eV, and the measured work function changed to 5.51 eV. As a result, the Schottky barrier height of Pt/ZnO(0 0 0 1) interface was 1.11 eV.  相似文献   

16.
We use first-principles density functional theory-based calculations in the analysis of the interaction of H2O with (1 0 0), (1 1 0) and (1 1 1) surfaces of TiN, and develop understanding in terms of surface energies, polarity of the surface and chemistry of the cation, through comparison with H2O adsorption on ZrN. While water molecule physisorbs preferentially at Ti site of (1 0 0) and (1 1 1) surfaces, it adsorbs dissociatively on (1 1 0) surface of TiN with binding stronger than almost 1.32 eV/molecule. Our analysis reveals the following general trends: (a) surfaces with higher energies typically lead to stronger adsorption, (b) dissociative adsorption of H2O necessarily occurs on a charge neutral high energy surface and (c) lower symmetry of the (1 1 0) plane results in many configurations of comparable stability, as opposed to the higher symmetry (1 0 0) and (1 1 1) surfaces, which also consistently explain the results of H2O adsorption on MgO available in literature. Finally, weaker adsorption of H2O on TiN than on ZrN can be rationalized in terms of greater chemical stability of Ti arising from its ability to be in mixed valence.  相似文献   

17.
The ultrasonic speeds, u and viscosities, η of binary mixtures of formamide (FA) with ethanol, 1-propanol, 1,2-ethanediol, and 1,2-propanediol, including those of pure liquids, over the entire composition range were measured at 293.15, 298.15, 303.15, 308.15, 313.15, and 318.15 K. From the experimental values of u and η, the deviations in isentropic compressibility, Δks, in ultrasonic speed, Δu, and in viscosity, Δη were calculated. The variation of these parameters with composition and temperature of the mixtures are discussed in terms of molecular interaction in these mixtures. The observed trends in Δks values indicate the presence of specific interactions between FA and alkanol molecules. The Δks values follow the order: ethanol < 1-propanol < 1,2-propanediol < 1,2-ethanediol. It is observed that the Δks values depend upon the number of hydroxyl groups and alkyl chain length in these alkanol molecules. Furthermore, the free energies, ΔG, enthalpies, ΔH and entropies, ΔS of activation of viscous flow have also been obtained by using Eyring viscosity equation and their dependence on composition of the mixtures have been discussed.  相似文献   

18.
The oxidation of aniline at Cu(1 1 0) surfaces at 290 K has been studied by XPS and STM. A single chemisorbed product, assigned to a phenyl imide (C6H5N(a)), is formed together with water which desorbs. Reaction with preadsorbed oxygen results in a maximum surface concentration of phenyl imide of 2.8 × 1014 mol cm−2 and a surface dominated by domains of three structures described by , and unit meshes. However, concentrations of phenyl imide of up to 3.3 × 1014 mol cm−2 were obtained from the coadsorption of aniline and dioxygen (300:1 mixture) resulting in a highly ordered biphasic structure with and domains. Comparison of the STM and XPS data shows that only half the phenyl imides at the surface are imaged. Pi-stacking of the phenyl rings is proposed to account for this observation.  相似文献   

19.
An X-ray photoelectron spectroscopy (XPS) study was undertaken of the water/Cu(1 1 0)-system finding non-dissociative adsorption on clean Cu(1 1 0) at temperatures below 150 K. Thermally induced dissociation of D2O is observed to occur above 150 K, similar to the H2O/Ru(0 0 1) system, with an experimentally derived activation barrier of 0.53-0.56 eV which is very close in magnitude to the derived activation barrier for desorption of 0.50-0.53 eV. X-ray and electron induced damage to the water overlayer was quantified and used to rationalize the results of a recent XPS study of the water/Cu(1 1 0)-system where partial dissociation was observed already at 90 K.  相似文献   

20.
We observed four kinds of adsorbed NO molecules on Pt(9 9 7) at 11 K using infrared reflection absorption spectroscopy (IRAS). The peaks at 1690, 1484 and 1615 cm−1 are assigned to the N-O stretching modes of the on-top site and the hollow site on the terrace and the bridge site at the step, respectively. The 1385 cm−1 peak is observed below ∼70 K. We assign the 1385 cm−1 peak to the hollow site of the (1 1 1) microfacet at the step or the lower-terrace hollow site nearest to the step. By heating, site-to-site hopping to the more stable site occurs and the relative stability of four adsorption sites can be determined.  相似文献   

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