Reaction kinetics investigation of 1‐fluoro‐2,4‐dinitrobenzene with substituted anilines in ethyl acetate–methanol mixtures using linear and nonlinear free energy relationships

Aromatic nucleophilic substitution reaction of 1‐fluoro‐2,4‐dinitrobenzene with para‐substituted and meta‐substituted anilines was kinetically investigated in the mixtures of ethyl acetate and methanol at room temperature. The correlation of second‐order rate coefficients with Hammett's substituent constants yields a fairly linear straight line with negative slope in different mole fractions of ethyl acetate–methanol mixtures. The measured rate coefficients of the reaction demonstrated a dramatic variation in ethyl acetate–methanol mixtures with the increasing mole fraction of ethyl acetate. Linear free energy relationship (LFER) investigations confirm that polarity has a major effect on the reaction rate whereas the hydrogen‐bonding ability of the media has a slight effect on it. Nonlinear free energy relationship based on preferential solvation hypothesis showed differences between the microsphere solvation of the solute and the bulk composition of the solvents, and non‐ideal behavior is observed in the trend of the rate coefficients, which cover the LFER results. Copyright © 2011 John Wiley & Sons, Ltd.     

Bounds for free energy derivatives using renormalization group methods

The free energy of a thermodynamic system is known to be a concave function of the temperature. This fact is used, together with some results due to Fisher, to deduce bounds on the internal energy of the two-dimensional Ising model, given reasonably accurate upper and lower bounds on the free energy. These free energy bounds are derived from renormalization group transformations. Unfortunately, the numerical accuracy of the bounds on the internal energy is poor. The reasons for the failure are discussed.     

Solvophobic effects and relationships between the Gibbs energy and enthalpy for the solvation process

An approach is suggested to describe the solvophobic effects in various solvents, qualitatively and quantitatively. We analyzed the relationships between the Gibbs energies and enthalpies of solvation of alkanes in various solvents on the basis of existing experimental data. It is shown that for a large group of solvents, there is a linear correlation between the two quantities. Other solvents, primarily self‐associated, show deviations from this line. These deviations are always positive, leading to a decrease in solubility, and can be used as a measure of the strength of the solvophobic effects. It is also shown that the solvophobic effects is not the only factor determining the solubility, even for alkane solutes. The magnitudes of contributions of the solvophobic effect into the Gibbs energies of solvation of various compounds in monohydric alcohols are determined. These magnitudes are found to be linearly correlated with a characteristic molecular volume of a solute. The slope of correlation grows up with the concentration of hydrogen bonds in the liquid solvent. Copyright © 2011 John Wiley & Sons, Ltd.     

能量公设与自由能判据的普遍化形式

从能量公设的角度论述了自由能及其判据的普遍化形式,并对其本质内涵进行了讨论．讨论认为：热力学系统中目由能的一般形式是与N种功类型相关的各种能形式之和,对孤立物体系在温度不变的情形下,不可逆过程总是导致总自由能的减少．通过实例说明了普遍化形式自由能判据的应用．     

Kinetics of alkaline hydrolysis of p‐substituted benzylidenemalononitriles in 50% aqueous acetonitrile: substituent effects and quantification of the electrophilic reactivity

The rate constants of the reaction of p‐X‐substituted benzylidenemalononitriles 1a , 1b , 1c , 1d , 1e , 1f , 1g , 1h with hydroxide ion were measured in 50% water–50% acetonitrile at 20 °C. The experimental kinetic data reveal that the points pertaining to electron donating substituted compounds (X = Me, OMe and NMe₂) exhibit negative deviations from the Hammett plot. However, the Yukawa–Tsuno plot for the same rate constants resulted in a good straight line with an excellent correlation coefficient (r² = 0.9916) and an r value of 1.15. Possible ground‐state stabilization through resonance interactions has been suggested to explain the origin of the nonlinear Hammett plot. On the basis of the relationship between E and σ_p⁺, the electrophilicity parameter E of some benzylidenemalononitriles 1c and 1e , 1f , 1g , 1h has been evaluated. More importantly, the three compounds 1f (E = ?7.90), 1g (E = ?7.80) and 1h (E = ?7.55) exhibit high electrophilicities that compare well with that of 4,6‐dinitrobenzoselenadiazole (E = ?7.40), a compound which has a general behaviour representative for the superelectrophilic dimension. We have shown that the second‐order rate constants calculated from Mayr's approach for the reaction of 1a , 1b , 1c , 1d , 1e , 1f , 1g , 1h with hydroxide ion do not agree with the available experimental data. On the other hand, a good linear correlation between log k_exp and log k_calc has been observed and discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

Simple inequality for the free energy of disordered systems

It is proved that the free energy of a disordered system described by a quadratic form in Bose or Fermi operators with random coefficients, calculated in the simplest approximation for the associated eigenvalue problem, gives the upper (Bose case) and lower (Fermi case) bounds for the exact free energy.     

关于Young-Laplace公式的吉布斯自由能证明

对于为论证球形液滴附加压强的Young-Laplace公式而设计的一个理想实验,有文献试图借助吉布斯自由能函数进行证明,本文给出符合这一条件的证明方法.     

抑制剂Benzamidine与胰岛素作用机制的分子动力学和结合自由能计算研究

氢键和极性相互作用在抑制剂-蛋白结合专一性识别过程中起到重要作用. 抑制剂Benzamidine(BEN)与胰岛素trypsin相互作用机制的阐明有助于胰岛素高效抑制剂的研发.本文采用分子动力学模拟和MM-PBSA(molecular mechanics-Poisson Boltzmann surface area)从原子层次上研究BEN与胰岛素的结合模式.结果表明抑制剂BEN的脒基不仅与Asp189的羰基产生静电相互作用,而且与残基Ser190和Gly214形成氢键相互作用.基于残基能量分解的计算表明抑制剂的苯基与残基His58, Cys191, Gln192, Trp211, Gly212和Cys215形成有利于抑制剂结合的疏水性相互作用.期望当前的研究能为胰岛素有效抑制剂的研发提供重要的理论指导.     

抑制剂Benzamidine与胰岛素作用机制的分子动力学和结合自由能计算研究

氢键和极性相互作用在抑制剂-蛋白结合专一性识别过程中起到重要作用.抑制剂Benzamidine(BEN)与胰岛素trypsin相互作用机制的阐明有助于胰岛素高效抑制剂的研发.本文采用分子动力学模拟和MM-PBSA(molecular mechanics-Poisson Boltzmann surface area)从原子层次上研究BEN与胰岛素的结合模式.结果表明抑制剂BEN的脒基不仅与Asp189的羰基产生静电相互作用,而且与残基Ser190和Gly214形成氢键相互作用.基于残基能量分解的计算表明抑制剂的苯基与残基His58,Cys191,Gln192,Trp211,Gly212和Cys215形成有利于抑制剂结合的疏水性相互作用.期望当前的研究能为胰岛素有效抑制剂的研发提供重要的理论指导.     

Kinetic studies of the reaction of phenacyl bromide derivatives with sulfur nucleophiles

The reaction of the substituted phenacyl bromides 1a–e and 2a–e with thioglycolic acid 3 and thiophenol 6 in methanol underwent nucleophilic substitution S_N2 mechanism to give the corresponding 2‐sulfanylacetic acid derivatives 4a–e, 5a–e and benzenethiol derivatives 9a–e, 10a–e. The reactants and products were identified by mass spectra, infrared and nuclear magnetic resonance. We measured the kinetics of these reactions conductometrically in methanol at a range of temperatures. The rates of the reactions were found to fit the Hammett equation and correlated with σ‐Hammett values. The ρ values for thioglycolic acid were 1.22–1.21 in the case of 4‐substituted phenacyl bromide 1a–e, while in the case of the nitro derivatives 2a–e they were 0.39–0.35. The ρ values for thiophenol were 0.97–0.83 in the case of 4‐substituted phenacyl bromide 1a–e, while in the case of the nitro derivatives 2a–e they were 0.79–0.74. The Brønsted‐type plot was linear with a α = ?0.41 ± 0.03. The kinetic data and structure‐reactivity relationships indicate that the reaction of 1a–e and 2a–e with thiol nucleophiles proceeds by a concerted mechanism. The plot of log k₄₅ versus log k₃₀, the plot log(k_x,3‐NO2/k_H) versus log(k_x/k_H), and the Brønsted‐type correlation indicate that the reactions of the thiol nucleophiles with the substituted phenacyl bromides 1a–e and 2a–e are attributed to the electronic nature of the substituents. Copyright © 2011 John Wiley & Sons, Ltd.     

Investigation of magnetic field effect on surface and finite-site free energy in one-dimensional Ising model of nanosystems

We investigate a one-dimensional (1-D) Ising model for finite-site systems. The finite-site free energy and the surface free energy are calculated via the transfer matrix method. We show that, at high magnetic fields, the surface free energy has an asymptotic limit. The absolute surface energy increases when the value of f (the ratio of magnetic field to nearest-neighbor interactions) increases, and for f?≥?10 approaches a constant value. For the values of f?≥?0.2, the finite-site free energy also increases, but slowly. The thermodynamic limit in which physical properties approach the bulk value is also explored.     

Interfacial free energy anisotropy driven faceting of precipitates

Abstract

During solid–solid precipitation, interface free energy anisotropy is known to drive faceting of precipitates. In this paper, using a recently developed phase field formulation based on higher order tensor terms, we develop and implement a family of phase field models and indicate the parameter choices which lead to faceted precipitate morphologies. We also indicate how to choose the parameters given either the known precipitate morphology or the interfacial free energy anisotropy. Specifically, we study the faceting of precipitates in systems with cubic and hexagonal anisotropies; in 2 and 3D implementation of our phase field model, the precipitates do show facets in accordance with the Wulff plot – including cases where the Wulff plot predicts facets made up of more than one family of planes. We also indicate the possible extensions of our model to study other problems of interest.     

Surface free energy of non-stick coatings deposited using closed field unbalanced magnetron sputter ion plating

Semiconductor IC packaging molding dies require wear resistance, corrosion resistance and non-sticking (with a low surface free energy). The molding releasing capability and performance are directly associated with the surface free energy between the coating and product material. The serious sticking problem reduces productivity and reliability. Depositing TiN, TiMoS, ZrN, CrC, CrN, NiCr, NiCrN, CrTiAlN and CrNiTiAlN coatings using closed field unbalanced magnetron sputter ion plating, and characterizing their surface free energy are the main object in developing a non-stick coating system for semiconductor IC molding tools. The contact angle of water, diiodomethane and ethylene glycol on the coated surfaces were measured at temperature in 20 °C using a Dataphysics OCA-20 contact angle analyzer. The surface free energy of the coatings and their components (dispersion and polar) were calculated using the Owens-Wendt geometric mean approach. The surface roughness was investigated by atomic force microscopy (AFM). The adhesion force of these coatings was measured using direct tensile pull-off test apparatus. The experimental results showed that NiCrN, CrN and NiCrTiAlN coatings outperformed TiN, ZrN, NiCr, CiTiAlN, CrC and TiMoS coatings in terms of non-sticking, and thus have the potential as working layers for injection molding industrial equipment, especially in semiconductor IC packaging molding applications.     

吉布斯自由能的农业应用和生物学意义

吉布斯自由能作为基本力学函数,在农业和生物学中有着重要的应用,在现代农业中,由吉布斯自由能的水势要概念,已成为判断农业系统水份动转的主要判据;在生物学中,吉布斯自由能作为生命体系赖以生存的能量,直接维持和驱动着生命体系的运转,本文讨论了吉布斯自由能的农业应用和生物学意义。     

利用扩展系综法计算水的自由能

利用扩展系综法得到了正则系综下水的TIP4P模型的自由能值为-21．485±0．035kJ/mol， 并与其他方法所得的结果作了比较.提出了选择该方法中关键参数(平衡因子)的有效方法， 并讨论了该方法的可移植性. 关键词： 自由能 TIP4P水模型 扩展系综 分子动力学模拟 水分子团     

Synthetic popularity reflects chemical reactivity

Large and diverse databases of chemical reactions contain statistically significant information about the propensities of molecules to undergo specific chemical transformations. It is shown that this information can be quantified to reflect reaction thermodynamics/kinetics and can be used to construct primitive (yet accurate) reactivity indices from the counts of reported reactions involving molecules/molecular positions of interest. These indices correlate with frontier orbital (FO) populations or Hammett σ and ρ parameters for a range of reactions involving aromatic substrates. These findings suggest that large chemical databases are not only a historical repository of chemical knowledge but also tools with which one can make useful chemical predictions. Copyright © 2009 John Wiley & Sons, Ltd.     

Failure of free energy relation under non-Markovian heat bath temperature change

We investigate the free energy relation for a system contacting with a non-Markovian heat bath and find that the validity of the relation sensitively depends on the non-Markovian memory effect, which is especially related to the initial preparation effect. This memory effect drives the statistical distribution of the system out of the initial preparation, even if the system starts from an equilibrium state. This leads to the violation of the free energy relation. A possible way of eliminating this memory effect is proposed.     

Surface free energy of polypropylene and polycarbonate solidifying at different solid surfaces

Advancing and receding contact angles of water, formamide, glycerol and diiodomethane were measured on polypropylene (PP) and polycarbonate (PC) sample surfaces which solidified at Teflon, glass or stainless steel as matrix surfaces. Then from the contact angle hystereses (CAH) the apparent free energies of the surfaces were evaluated. The original PP surface is practically nonpolar, possessing small electron donor interaction (), as determined from the advancing contact angles of these liquids. It may result from impurities of the polymerization process. However, it increases up to 8-10 mJ/m² for PP surfaces contacted with the solids. The PC surfaces both original and modified show practically the same . No electron acceptor interaction is found on the surfaces.The of modified PP and PC surfaces depend on the kind of probe liquid and contacted solid surface. The modified PP values determined from CAH of polar liquids are greater than that of original surface and they increase in the sequence: Teflon, glass, stainless steel surface, at which they solidified. No clear dependence is observed between and dielectric constant or dipole moment of the polar probe liquids. The changes in of the polymer surfaces are due to the polymer nature and changes in its surface structure caused by the structure and force field of the contacting solid. It has been confirmed by AFM images.     

关于二元混合物体系的偏摩尔吉布斯自由能的表达式

利用Gibbs-Duhem方程证明了偏摩尔自由能的一个计算公式.