四唑及其衍生物的理论研究Ⅷ: 硝氨四唑衍生物的从头算

运用从头计算法,在HF/6-31G^*水平下,全优化计算了7种硝氨四唑衍生物的分子几何和电子结构。结果表明,标题物的四唑环近似为平面构型;2H式中性分子的芳香性大于相应的1H式异构体。5-硝氨-1H四唑分子内氢键使硝氨基与环共面;其余标题物中硝氨基与环垂直。不同水平下的总能量计算表明,标题物中电子相关效应显著;1H式中性分子较2H式的能量高,5-硝氨四唑负离子在三个负离子中最稳定。根据电荷分布阐明了四唑环质子化位置和标题物与金属的配位方式。此外还计算了各标题物的红外光谱及热力学性质。     

A conductance study of the association of alkali cations with 1,13-dibenzo-24-crown-8 in acetonitrile

A conductance study concerning the association of Na⁺, K⁺, Rb⁺, and Cs⁺ with 1,13-dibenzo-24-crown-8 in acetonitrile has been carried out at 35, 30, 25, 20, and 15°C. The observed molar conductivities were found to decrease significantly for mole ratios less than unity. A model involving 11 stoichiometry has been used to analyze the conductivity data. The stability constant, K, and the molar conductivity _C for each 11 complex were determined from the conductivity data by using a nonlinear least squares curve fitting procedure. The binding sequence, based on the value of log K at 25°C, is found to be Rb⁺>Cs⁺>K⁺>Na⁺. Values of H^o and S^o are reported and their significance is discussed.     

Cure behavior of epoxy resin/MMT/DETA nanocomposite

The Flory's gelation theory, non-equilibrium thermodynamic fluctuation theory and Avrami equation have been used to predict the gel time t _g and the cure behavior of epoxy resin/organo-montmorillonite/diethylenetriamine intercalated nanocomposites at various temperatures and organo-montmorillonite loadings. The theoretical prediction is in good agreement with the experimental results obtained by dynamic torsional vibration method, and the results show that the addition of organo-montmorillonite reduces the gelation time t _gand increases the rate of curing reaction, the value of k, and half-time of cure after gelation point t_1/2 decreases with the increasing of cure temperature, and the value of n is ~2 at the lower temperatures (<60°C) and decreases to ~1.5 as the temperature increases, and the addition of organo-montmorillonite decreases the apparent activation energy of the cure reaction before gelation point, but has no apparent effect on the apparent activation energy of the cure reaction after gelation point. There is no special curing process required for the formation of epoxy resin/organo-montmorillonite/diethylenetriamine intercalated nanocomposite. This revised version was published online in July 2006 with corrections to the Cover Date.     

Application of a chemical equilibrium model to thermodynamic functions of transfer of alcohols from water to aqueous surfactants

In ternary aqueous solutions, hydrophobic solutes such as alcohols tend to aggregate with surfactants to form mixed micelles. These systems can be studied by meas of the functions of transfer of hydrophobic solutes from water to aqueous solutions of surfactant. These thermodynamic functions often go through extrema in the critical micellar concentration (CMC) region of the surfactant. A simple model based on interactions between surfactant and hydrophobic solute monomers, on the distribution of the hydrophobic solute between water and the micelles and on the shift in the CMC induced by the hydrophobic solute, can simulate the magnitude and trends of the transfer functions using parameters which are mostly derived from the binary systems. In order to check the model more quantitatively, volumes and heat capacities of transfer of alcohols from water to aqueous solutions of a nonionic surfactant, octyldimethylamine oxide, were measured. A quantitative agreement was achieved with three adjustable parameters. Good fits are also obtained for the transfers to the ionic surfactants, octylamine hydrobromide and sodium dodecylsulfate. When the equilibrium displacement contribution is small, the distribution constants and the partial molar properties of the alcohols in the micellar phase agree well with the parameters obtained with similar models.     

Studies on Thermodynamics Features of the Interaction between Imidacloprid and Bovine Serum Albumin

At different temperatures, the interactions between imidacloprid （IMI） and bovine serum albumin （BSA） were investigated with a fluorescence quenching spectrum, a synchronous fluorescence spectrum, a three-dimensional fluorescence spectrum and an ultraviolet-visible spectrum. The average values of bonding constants （KLB： 3.424 × 10^4 L,mol^-1）, thermodynamic parameters （△H： 5.188 kJ,mol^-1, △G^（○—）：-26.36 kJ,mol^-1, △S： 103.9 J,K^-1,mol^-1） and the numbers of bonding sites （n： 1.156） could be obtained through Stern-Volmer, Lineweaver-Burk and ther- modynamic equations. It was shown that the fluorescence of BSA could be quenched for its reactions with IMI to form a certain kind of new compound. The quenching belonged to a static fluorescence quenching, with a non-radiation energy transfer happening within a single molecule. The thermodynamic parameters agree with △H〉 0, △S〉0 and△G^（○-）〈0, suggesting that the binding power between IMI and BSA should be mainly a hydrophobic interaction.     

Chemistry of borate in salt lake brine (XXXIV)

The crystallization processes of hydrated Mg-borates, boric, magnesium hydroxide and Mg-oxychloride from MgO-B₂O₃-18%MgCl₂-H₂O supersaturated solution at 20°C have been studied by kinetic method. The crystallization solid phases were characterized by X-ray powder diffraction, IR spectra, thermal analysis and chemical analysis. The liquid-solid phase diagram of thermodynamic nonequilibrium state has been given. In this phase diagram, there exist eight crystallization fields, boric acid(H₃BO₃), trigomagneborite(MgO · 3B₂O₃ · 7.5H₂O, MgO · 3B₂O₃ · 7H₂O), hungchaoite(MgO · 2B₂O₃ · 9H₂O), inderite(2MgO · 3B₂O₃ · 15H₂O), chloropinnoite(2MgO · 2B₂O₃ · MgCl₂ · 14H₂O), magnesium hydroxide(Mg(OH)₂) and magnesium oxychloride (5Mg(OH)₂ · MgCl₂ · 8H₂O).     

Thermochemistry of the solid complex Gd(Et<Subscript>2</Subscript>dtc)<Subscript>3</Subscript>(phen)

Summary A ternary solid complex Gd(Et₂dtc)₃(phen) has been obtained from reactions of sodium diethyldithiocarbamate (NaEt₂dtc), 1,10-phenanthroline (phen) and hydrated gadolinium chloride in absolute ethanol. The title complex was described by chemical and elemental analyses, TG-DTG and IR spectrum. The enthalpy change of liquid-phase reaction of formation of the complex, Δ_rH^Θ_m(l), was determined as (-11.628±0.0204) kJ mol^-1 at 298.15 K by a RD-496 III heat conduction microcalorimeter. The enthalpy change of the solid-phase reaction of formation of the complex, Δ_rH^Θ_m(s), was calculated as (145.306±0.519) kJ mol^-1 on the basis of a designed thermochemical cycle. The thermodynamics of reaction of formation of the complex was investigated by changing the temperature of liquid-phase reaction. Fundamental parameters, the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A), the reaction order (n), the activation enthalpy (Δ_rH^Θ_≠), the activation entropy (Δ_rS^Θ_≠), the activation free energy (Δ_rG^Θ_≠) and the enthalpy (Δ_rH^Θ_≠), were obtained by combination of the thermodynamic and kinetic equations for the reaction with the data of thermokinetic experiments. The constant-volume combustion energy of the complex, Δ_cU, was determined as (-18673.71±8.15) kJ mol^-1 by a RBC-II rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δ_cH^Θ_m, and standard enthalpy of formation, Δ_fH^Θ_m, were calculated to be (-18692.92±8.15) kJ mol^-1 and (-51.28±9.17) kJ mol^-1, respectively.     

Experimental and Theoretical Study of the Effect of Moisture on Methane Adsorption and Desorption by Activated Carbon at 273.5 K

Adsorption and desorption of methane by activated carbon (AC) at constant temperature and at various pressures were investigated. The effect of moisture was also studied. A volumetric method was used, up to 40 bar, at a temperature of 273.5 K. Results of a dry AC sample were compared with those obtained from a moist sample and two different ACs with different physical and surface properties were used. As expected, the results showed that the existence of moisture, trapped in the AC pores, could lead to a decrease in the amount of methane adsorbed and a decrease in the amount of methane delivered during desorption. To model the experimental results, a large variety of adsorption isotherms were used. The regressed parameters for the adsorption isotherms were obtained using the experimental data generated in the present study. The accuracy of the results obtained from the different adsorption isotherms was favorably compared.     

乙醇和甲苯组成的最低共沸混合物热力学性质的研究

The molar heat capacity of the azeotropic mixture composed of ethanol and toluene was measured by a high precision adiabatic calorimeter from 80 to 320 K. The glass transition and phase transitions of the azeotropic mixture were determined based on the heat capacity measurements. A glass transition at 103.350 K was found. A solid-solid phase transition at 127.282 K, two solid-liquid phase transitions at 153.612 and 160.584 K were observed, which correspond to the transition of metastable crystal to stable crystal of ethanol and the melting of ethanol and toluene, respectively. The thermodynamic functions and the excess ones of the mixture relative to the standard temperature 298.15 K were derived based on the relationships of the thermodynamic functions and the function of the measured heat capacity with respect to temperature.     

Calorimetric study of thermodynamics of production of polybutene-1, polypentene-1, 4-methylpentene-1 and properties of reagents between 0 and 670 K

The heat capacitiesC ₀ ^p of polybutene-1, polypentene-1, poly-4-methylpentene-1 and 4-methylphentene-1 were studied calorimetrically from 6 to (500–700) K. Temperatures, enthalpies of melting of various crystalline forms and the parameters of the glass transition were determined. The thermodynamic functionsH ⁰(T)?H⁰(0), S⁰(T) andG ⁰(T)?H⁰ (0) were calculated between 0 K and (500–700) K. From the calorimetric values obtained and literature data, the thermodynamic characteristics of the following processes were estimated for the corresponding alkenes-1, andcis-andtrans-alkenes-2: the polymerization of alkenes-1, the monomer-isomerization polymerization ofcis- andtrans-alkenes-2 to polyaklenes-1 and the isomerization ofcis- andtrans-aklenes-2 to alkenes-1 in the same temperature interval at standard pressure.