Importance of the Debye interaction in organic solutions: Henry's law constants for polar liquids in nonpolar solvents and vice versa

Henry's law constants have been determined for -butyrolactone (BL), ethyl acetate (EA), and 2-methyl-3-pentanol (MEP) in mixtures of iso-octane (ISO) and toluene (TOL), for BL, EA, TOL, and ISO in cinnamaldehyde (CIN) and for TOL and ISO in each other and in BL. From these data and published vapor pressures, the activity coefficients at infinite dilution and the standard molar Gibbs free energy of transfer, G ₂ ⁰ of the solutes from dilute solution in ISO to dilute solution in each solvent medium have been calculated. The different behavior patterns of BL and EA are attributed to differences in their abilities to exist in different conformations possessing different dipole moments. For polar solutes, G ₂ ⁰ decreases with increasing polarizability of the solvent and with increasing dipole moment of the solute, suggesting increased contributions from dipole-induced dipole (Debye) interactions. The sigmoidal plot of G ₂ ⁰ against the change in pair potential energy calculated from the classical expressions suggests that G ₂ ⁰ seriously underestimates the strength of the Debye interactions in comparison with the London interactions.     

掺杂电活性离子聚吡咯膜内的电荷传输

用循环伏安法和计时库仑法研究了掺杂亚铁氰化钾离子的聚哟咯膜内的电荷传输问题。实验结果表明，聚吡咯膜内的电荷传递可以处理成电子在膜内的扩散模型，电荷传递速度可以 用电子表观扩散系数（Ｄａｐｐ）来表征。Ｄａｐｐ的大小由聚合物膜的结构、电活怀离子之间的过及对离了在膜中的运动决定。     

Investigations of precipitates in heat treated AgPd30/CuSn6 layers

The subject of the investigations are precipitation zones, which grew as a result of chemical diffusion in AgPd30/CuSn6 bimetals. These precipitation zones have been characterized by metallography, electron probe microanalysis and x-ray diffraction. The growth of precipitation zones in the plating layer and in the substrate layer in dependence on time have been determined. The use of x-ray diffraction alone for the identification of the precipitates could not supply satisfying results in every case. This problem was solved by the application of electron probe microanalysis using a correction method, which allows the estimation of the chemical composition of small particles.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday     

The time-local view of nonequilibrium statistical mechanics. I. Linear theory of transport and relaxation

The various approaches to nonequilibrium statistical mechanics may be subdivided into convolution and convolutionless (time-local) ones. While the former, put forward by Zwanzig, Mori, and others, are used most commonly, the latter are less well developed, but have proven very useful in recent applications. The aim of the present series of papers is to develop the time-local picture (TLP) of nonequilibrium statistical mechanics on a new footing and to consider its physical implications for topics such as the formulation of irreversible thermodynamics. The most natural approach to TLP is seen to derive from the Fourier-Laplace transform ) of pertinent time correlation functions, which on the physical sheet typically displays an essential singularity at z= and a number of macroscopic and microscopic poles in the lower half-plane corresponding to long- and short-lived modes, respectively, the former giving rise to the autonomous macrodynamics, whereas the latter are interpreted as doorway modes mediating the transfer of information from relevant to irrelevant channels. Possible implications of this doorway mode concept for socalled extended irreversible thermodynamics are briefly discussed. The pole structure is used for deriving new kinds of generalized Green-Kubo relations expressing macroscopic quantities, transport coefficients, e.g., by contour integrals over current-current correlation functions obeying Hamiltonian dynamics, the contour integration replacing projection. The conventional Green-Kubo relations valid for conserved quantities only are rederived for illustration. Moreover, may be expressed by a Laurent series expansion in positive and negative powers ofz, from which a rigorous, general, and straightforward method is developed for extracting all macroscopic quantities from so-called secularly divergent expansions of as obtained from the application of conventional many-body techniques to the calculation of . The expressions are formulated as time scale expansions, which should rapidly converge if macroscopic and microscopic time scales are sufficiently well separated, i.e., if lifetime (memory) effects are not too large.     

Diffusion current on a nonuniform electrode: Calculation with integral equations

Identity of mathematical problems concerning calculation of the distribution of reactants’ concentrations and the current near the surface of a nonuniform (strip) electrode and distribution of displacements and forces in the case of an elastic layer “antiplane” deformation caused by the punch action. Formulas for calculating the current at a strip electrode are derived for various ratios between the electrode width and the diffusion layer thickness by means of asymptotic methods designed for calculating problems of mechanical contact interactions. It is noted that calculations of the diffusion current for involved activity distributions at the electrode surface may benefit from asymptotic methods of mechanics of contact interactions.     

Effect of NaOH and NaCl on the disodiumn-decane phosphonate micellar aggregation number

The diffusion coefficient of disodiumn-decane phosphonate micelles was studied by polarography at 25°C in NaCl and in NaOH solutions, and the size and aggregation number of the micelles was computed as a function of Na⁺ concentration. All other conditions being equal, the addition of NaCl produces micelles with an aggregation number one order of magnitude larger than the NaOH addition. This is due to the increase of the effective charge per micellized head group produced by the reaction of OH- with the hydrolized head groups which are mainly present as-PO₃H- in the micellar Stern layer.     

Drift tube investigations on the reactions of O 2 + with CH4 and of CO 2 + with NO in various buffer gases

The influence of internal excitation on the reactions of O ₂ ⁺ + CH₄ and of CO ₂ ⁺ + NO has been investigated using a slow flow drift tube. The rate coefficients for these reactions obtained as a function of relative kinetic energy in various buffer gases like He, Ne, Ar, and Kr showed higher values under conditions where the internal excitation of the reactant ions was enhanced. For both reactions the lowest reactivity at all kinetic energies was observed to occur in He, indicating that He is the least effective buffer for collisionally inducing internal excitation of molecular ions.     

室温熔盐二(三氟甲基磺酸酰)亚胺锂-尿素体系的分子动力学模拟

应用分子动力学模拟了25 ℃和50 ℃时新型室温熔盐二(三氟甲基磺酸酰)亚胺锂[LiN(SO2CF3)2, LiTFSI]与尿素(摩尔比为1:3.6)体系的结构与动力学性质. 在两个温度下体系的微观结构基本相同, Li+的配位数约为5, 且都是与溶剂和阴离子中的氧原子发生配位. 对TFSI-的研究表明, 每个TFSI-只提供四个氧中的一个与Li+配位; 而且在Li+的配位层中, TFSI-具有顺、反和gauche 等不同的构象, 并且不同构象出现的几率会随着温度的改变而改变.     

Solubility of gases in liquids. 18. High-precision determination of Henry fugacities for argon in liquid water at 2 to 40°C

The solubility of argon in pure liquid water was measured at ca. 100 kPa and from 2 to 40°C using an analytical method characterized by an imprecision of about ±0.05%. From the experimental results, Henry fugacities H _2,1 (T,P _s,1 ) (also known as Henry's Law constants or Henry coefficients) at the vapor pressure P _s,1 of water as well as Ostwald coefficients L _2,1 at infinite dilution were obtained. Measurements were made at roughly 0.5°C and/or 1° intervals between 2 and 8°C (region I), and at 5°C intervals above 10°C (region II). A difference plot lnH _2,1 /T suggests an unusual temperature dependence in region I, i.e., between 2 and 8°C. Because of this, the data were treated separately in two parts corresponding to these two regions. Our results are compared with the recent high-precision data of Krause and Benson (Henry fugacities), and with calorimetrically determined quantities (enthalpies and heat capacities of solution). Finally, experimental results are compared with values calculated via scaled particle theory.Communicated in part at the 2^nd International Symposium on Solubility Phenomena in Newark, New Jersey, August 12–15, 1986, and at the 4^th ISSP in Troy, New York, July 20–August 3, 1990.     

A New Tool in Peptide Engineering: A Photoswitchable Stilbene‐type β‐Hairpin Mimetic

Peptide secondary structure mimetics are important tools in medicinal chemistry, as they provide analogues of endogenous peptides with new physicochemical and pharmacological properties. The development, synthesis, photochemical investigation, and conformational analysis of a stilbene‐type β‐hairpin mimetic capable of light‐triggered conformational changes have been achieved. In addition to standard spectroscopic techniques (nuclear Overhauser effects, amide temperature coefficients, circular dichroism spectroscopy), the applicability of self‐diffusion measurements (longitudinal eddy current delay pulsed‐field gradient spin echo (LED‐PGSE) NMR technique) in conformational studies of oligopeptides is demonstrated. The title compound shows photoisomerization of the stilbene chromophore, resulting in a change in solution conformation between an unfolded structure and a folded β‐hairpin.