首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到10条相似文献,搜索用时 125 毫秒
1.
The supramolecular structure and dielectric properties of pure fluid methanol are modeled in the temperature range from melting point to supercritical state using the Quasichemical Model of the Nonideal Associated Solution (QCNAS). Two models of supramolecular structure are compared as regards their performance to reproduce experimental data on dielectric permittivity of methanol. The first model includes only chain-like aggregation while the second one takes into account both chain-like and cyclic methanol aggregates. Dielectric permittivity and dipole correlation factor of methanol are calculated in the temperature interval 177–593 K with pressure ranging from 0.1 to 20 MPa. Both models proved quite adequate in reproducing experimental data for pure methanol, but including cyclic aggregates of methanol is essential for consistency with the models for methanol mixtures. The thermodynamic and structural parameters of supramolecular aggregates are reported. Distribution functions of aggregates over size and structure are evaluated in the entire temperature range. Long supramolecular aggregates with long range molecular correlations extending far beyond the nearest coordination shells are revealed.  相似文献   

2.
Understanding the physical and chemical processes in which local interactions lead to ordered structures is of particular relevance to the realization of supramolecular architectures on surfaces. While spectacular patterns have been demonstrated on metal surfaces, there have been fewer studies of the spontaneous organization of supramolecular networks on semiconductor surfaces, where the formation of covalent bonds between organics and adatoms usually hamper the diffusion of molecules and their subsequent interactions with each other. However, the saturation of the dangling bonds at a semiconductor surface is known to make them inert and offers a unique way for the engineering of molecular patterns on these surfaces. This review describes the physicochemical properties of the passivated B-Si(111)-(√3x√3) R30° surface, that enable the self-assembly of molecules into a rich variety of extended and regular structures on silicon. Particular attention is given to computational methods based on multi-scale simulations that allow to rationalize the relative contribution of the dispersion forces involved in the self-assembled networks observed with scanning tunneling microscopy. A summary of state of the art studies, where a fine tuning of the molecular network topology has been achieved, sheds light on new frontiers for exploiting the construction of supramolecular structures on semiconductor surfaces.  相似文献   

3.
The inverse gas chromatography (IGC) method was used to characterize the hydrogen bond energies of chitin‐methanol and chitin‐ethanol. Surface Lewis acid‐base properties of the chitin were determined at the same time. Six solvents, trichloromethane, acetone, ether, tetrahydrofuran, methanol, and ethanol were used as polar probes for the IGC measuration. The hydrogen bond energies of chitin‐methanol and chitin‐ethanol were 23.3 and 21.3 kJ/mol, respectively. Because the linear relation of the plot of ?ΔHa s/AN* versus DN/AN* (DN and AN* are the Gutmann's donor and modified acceptor numbers of solvents) for the six probes was perfect, it can be concluded that the hydrogen bonds of chitin‐alcohols belong to Lewis acid‐base interactions. The hydrogen bonds were moderate hydrogen bonds.  相似文献   

4.
Ultrasonic technique, transport properties and related acoustical parameters of 1,4-dioxane and N,N-dimethyl formamide were prepared of different % compositions at variable temperatures using tetra alkyl ammonium iodide salts (R4NI) of 0.14 M, to investigate inter-ionic interactions, molecular interactions, molecular rearrangement, molecular association etc. The densities were measured by using magnetic float densitometer. Transport properties provide a deep and meaningful insight of various interactions taking place between the binary liquid mixtures with salts. We have observed the influence of small as well as large alkyl chain length (R4N+), and extract the information with respect to various kinds of intermolecular interactions such as dipole-dipole, dipole-induced dipole, solute-solvent, dispersive type and H-bonding interaction between the components. Such observations in the presence of specific molecular interactions of binary solutions and structural effects were analyzed on the basis of measured and derived thermo-dynamical parameters.  相似文献   

5.
H. Yilmaz  S. Güler 《Il Nuovo Cimento D》1998,20(12):1853-1861
Summary  In this study the viscosities of binary mixtures of methanol and water have been measured in the temperatures ranging from 15 to 45°C. The structural changes occurring as a consequence of molecular interactions in the solutions have been discussed in detail. Nevertheless, it would be of interest to see whether the information obtained from viscosity studies can be corroborated with that obtained from dielectric-constant data. With this aim, the present study on the dielectric behaviour of methanol-water binary solutions has been undertaken. The static dielectric constants, densities and refractive indices have been also measured on the methanol-water mixtures expressed by the mole fraction of methanol (0<x2<1). Excess dielectric constants, excess volumes, excess viscosities and excess Gibbs energies of activation of the viscous flow and Kirkwood correlation factors have been evaluated using experimental results since these calculations may lead to conclusions concerning the deviation of the system from an ideal-mixture behaviour.  相似文献   

6.
本文利用聚集型状态方程,克拉贝龙方程以及临界条件推出聚集活性参量方程.分析结果表明,医药的药理活性是可以用聚集活性参量予以定量表征.本文给出了某些医药的主要的药物成分,如氧化亚氮 乙醚、氯仿和水杨酸甲酯等嘛醉剂),一氧化氮(硝酸甘油)、乙醇胺(医药活性剂)和多巴胺(神经递质)的生物活性数据.实践经验表明,这些化学品分别在生命体的心血管系统、神经系统和免疫系统中起着重要的药理功能作用.这表明,本文研究的内容在医药学研究领域有其重要意义.  相似文献   

7.
In the present work, we have used a simple equation of state called the GMA EoS to calculate the density of three ionic liquid mixtures including 1-butyl-3-methylimidazolum hexafluorophosphate, [BMIM] [PF6] + methanol, 1-butyl-3-methylimidazolum tetrafluoroborate, [BMIM] [BF4] + methanol, and [BMIM] [BF4] + ethanol at different temperatures, pressures, and compositions. The isothermal compressibility, excess molar volumes, and excess Gibbs molar energy of these mixtures have been computed using this equation of state. The values of statistical parameters show that the GMA EoS can predict these thermodynamic properties very well within the experimental errors. The results show that isothermal compressibility of ionic liquids is lower than alcohols and the effect of temperature and pressure on the isothermal compressibility of ionic liquids is lower than alcohols. The excess molar volumes and excess molar Gibbs energy for these ionic liquid mixtures with alcohols are all negative at various temperatures and pressures over the whole composition range. The results have been interpreted in terms of intermolecular interactions and structural factors of the ionic liquids and alcohols.  相似文献   

8.
Infrared spectra of the ethanol–water and methanol–water mixtures in the mole fraction range of 0.1 to 0.9 were recorded in the attenuated reflection (ATR) mode. Traditionally, the hydrogen bonding of water with other molecules has been studied by investigation of the OH stretching band frequencies and intensities of water. However, in the case of alcohol–water mixtures, this procedure presents a problem due to the complete overlap of the hydroxyl absorptions from the alcohol and water. In the present study, we have adopted an alternative approach of understanding the ethanol–water and methanol–water hydrogen bonds through the analysis of the C-O stretching band. The intrinsic high intensity of the C-O band and nearly complete absence of its overlap with the water bands make it a good candidate for the study of hydrogen bonding interactions in alcohol–water mixtures. The integrated areas of the C-O stretching band versus mole fractions were plotted for both mixtures. In the case of methanol–water mixtures, the C-O stretching band area plot was linear, whereas such plot for the ethanol–water mixtures had two distinct slopes that switched at the 0.5 mole fraction. The C-O band plot areas were used to explain the molecular associations in the mixtures studied.  相似文献   

9.
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 Δκs, excess molar volume , viscosity deviation Δη and excess Gibb’s free energy of activation for viscous flow ΔGE 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.  相似文献   

10.
Static dielectric permittivity, density, viscosity, and refractive index of anisole (AN), methanol (MeOH), 1-propanol (1-PrOH) and binary mixtures of AN with MeOH and 1-PrOH at nine different concentrations, were measured at 303, 313 and 323 K temperatures. Measured properties of pure AN, MeOH and 1-PrOH were compared with literature values and they were found in good agreement. The investigation of binary mixtures showed a systematic change in static dielectric permittivity, density and viscosity with change in concentration of anisole in the mixture. Measured properties of liquid samples were used to calculate Kirkwood correlation factor and excess parameters such as excess dielectric permittivity, excess molar volume and excess viscosity. Determined parameters have been interpreted in terms of molecular interaction among the molecular species of the binary mixtures.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号