Effects of substituted ligands on the mobility of complexed anions

From conductance and viscosities measurements on Pr₄NCl, Et₄NBr, and AgNO₃ in acetonitrile and Et₃NBr in nitrobenzene, the Walden products of the anion at infinite dilution were determined in presence of various concentrations of substituted benzoic acids. From these data it was possible to compute the values of the Walden products of the once complexed anions and to estimate the order of magnitude of the Walden products of twice complexed anions. Stokes' law is not obeyed, and the Walden products are not proportional to the third root of the molar volume of the complexed ions, as a consequence of their lack of sphericity. The assumption that the drag force which acts on the ions is proportional to the volume of the substituents results in a linear expression between the reciprocals of the Walden products and the molar volume of the ligands. The experimental results fit this expression within the limits of the experimental errors, and the slopes of the lines are nearly the same for all the anions and for the two solvents studied here, namely, 2.5×10^–4 ohm-cm^–5 mole-cP^–1.     

Dynamic scaling of migration-driven aggregate growth

We study the kinetic behaviour of the growth of aggregates driven by reversible migration between any two aggregates. For a simple model with the migration rate K(i;j)=K′(i;j)∝i^uj^v at which the monomers migrate from the aggregates of size i to those of size j, we find that the aggregate size distribution in the system with u+v≤3 and u<2 approaches a conventional scaling form, which reduces to the Smoluchovski form in the u=1 case. On the other hand, for the system with u<2, the average aggregate size S(t) grows exponentially in the u+v=3 case and as (tlnt)^{1/(5-2u)} in another special case of v=u-2. Moreover, this typical size S(t) grows as t^{1/(3-u-v)} in the general u-2相似文献   

费托反应本征动力学中合成气分压对反应速率的影响

利用高通量动力学反应器测量了本征条件下钴基费托催化剂上反应物消耗速率rCO和产物生成速率rCH4随固定床床层的分布,并考察了它们在不同入口分压(p0CO,p0H2)条件下的变化.结果表明,入口氢碳比(H/C)0=p0H2/p0CO为影响速率的敏感外部变量,反应速率随(H/C)0的增加而加快;而合成气总压p0H2+CO则...     

Vapor-liquid equilibria for the nitrogen-isobutane system

Vapor-liquid equilibria have been investigated experimentally for the nitrogen-isobutane system at temperatures from 120 K to 220 K and at pressures up to 150 bar. Below 126.5 K, two liquid phases were observed as pressure was increased to near the vapor pressure of pure nitrogen. The equilibrium ratio of nitrogen in the binary system and the Henry’s law constants for nitrogen in isobutane were determined from experimental data. The experimental phase equilibrium data were correlated by means of the Peng-Robinson equation of state.     

Combining linear polarization spectroscopy and the Representative Layer Theory to measure the Beer–Lambert law absorbance of highly scattering materials

Visible and Near Infrared (Vis–NIR) Spectroscopy is a powerful non destructive analytical method used to analyze major compounds in bulk materials and products and requiring no sample preparation. It is widely used in routine analysis and also in-line in industries, in-vivo with biomedical applications or in-field for agricultural and environmental applications. However, highly scattering samples subvert Beer–Lambert law's linear relationship between spectral absorbance and the concentrations. Instead of spectral pre-processing, which is commonly used by Vis–NIR spectroscopists to mitigate the scattering effect, we put forward an optical method, based on Polarized Light Spectroscopy to improve the absorbance signal measurement on highly scattering samples. This method selects part of the signal which is less impacted by scattering. The resulted signal is combined in the Absorption/Remission function defined in Dahm's Representative Layer Theory to compute an absorbance signal fulfilling Beer–Lambert's law, i.e. being linearly related to concentration of the chemicals composing the sample. The underpinning theories have been experimentally evaluated on scattering samples in liquid form and in powdered form. The method produced more accurate spectra and the Pearson's coefficient assessing the linearity between the absorbance spectra and the concentration of the added dye improved from 0.94 to 0.99 for liquid samples and 0.84–0.97 for powdered samples.     

The minimum heat consumption for heat-driven binary separation processes with linear phenomenological heat transfer law

The optimal performance of heat-driven binary separation processes with linear phenomenological heat transfer law(q∝△(T-1)) is analyzed by taking the processes as heat engines which work between high-and low-temperature reservoirs and produce enthalpy and energy flows out of the system,and the temperatures of the heat reservoirs are assumed to be time-and space-variables.A numerical method is employed to solve convex optimization problem and Lagrangian function is employed to solve the average optimal contr...     

Analysis of RNA sequence structure maps by exhaustive enumeration I. Neutral networks

Summary Global relations between RNA sequences and secondary structures are understood as mappings from sequence space into shape space. These mappings are investigated by exhaustive folding of allGC andAU sequences with chain lengths up to 30. The computed structural data are evaluated through exhaustive enumeration and used as an exact reference for testing analytical results derived from mathematical models and sampling based on statistical methods. Several new concepts of RNA sequence to secondary structure mappings are investigated, among them that ofneutral networks (being sets of sequences folding into the same structure). Exhaustive enumeration allows to test several previously suggested relations: the number of (minimum free energy) secondary structures as a function of the chain length as well as the frequency distribution of structures at constant chain length (commonly resulting in generalized forms ofZipf's law).

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Analyse der Beziehungen zwischen RNA-Sequenzen und Sekundärstrukturen durch vollständige Faltung, 1. Mitt. Faltung, Neutrale Netzwerke

Zusammenfassung Die globalen Benziehungen zwischen RNA-Sequenzen und Sekundärstrukturen werden als Abbildungen aus einem Raum aller Sequenzen in einen Raum aller Strukturen aufgefaßt. Diese Abbildungen werden durch Falten aller binären Sequenzen desGC-undAU-Alphabets mit Kettenlängen bis zun=30 untersucht. Die berechneten Strukturdaten werden durch vollständiges Abzählen ausgewertet und als eine exakte Referenz zum Überprüfen analytischer Resultate aus mathematischen Modellen sowie zum Testen statistisch erhobener Proben verwendet. Einige neuartige Konzepte zur Beschreibung der Beziehungen zwischen Sequenzen und Strukturen werden eingehend untersucht, unter ihnen der Begriff derneutralen Netzwerke. Ein neutrales Netzwerk besteht aus allen Sequenzen, die eine bestimmte Struktur ausbilden. Vollständiges Abzählen ermöglicht beispielsweise die Bestimmung aller Strukturen minimaler freier Energie in Abhängigkeit von der Kettenlänge ebenso wie die Bestimmung der Häufigkeitsverteilungen der Strukturen bei konstanten Kettenlängen. Die letzteren folgen einer verallgemeinerten FormZipfschen Gesetzes.

     

Thermodynamics of ionic solid solutions: II. Discontinuous series: A new treatment of existing distribution data

A method of finding the activity coefficients of salts, anhydrous or hydrated, in binary solid solutions, described in an earlier paper as it applies to continuous series, has been applied to discontinuous series. The salts must differ with respect to only one ion. The method requires isothermal distribution data for equilibria between liquid (aqueous) and solid solutions in the ternary system consisting of the two salts and water. The following salt pairs were used for illustration: K(I/Br) at 0, 15, 25, 35, and 50°C., (NH₄/K)SCN at 0, 30, 60, and 90°C., (K/Tl)C10₃ at 10°C., and (NH₄/K)SO₃NH₂, (NH₄/K)Br, (Mg/Co)SO₄-7H₂O, and (Mn/Cu) SO₄.n H₂O-all at 25°C. Two kinds of behavior were noted and treated differently: systems in which the two series have the same, and those in which they have different crystal lattices. For two salts, A and B, which have the same lattice, and whose rational activity coefficients, f _A and f _B , can be described by 2-suffix Margules equations (regular solutions), lnf _A =B_sx _B ² and lnf _B =B_sx _A ² to be partially miscible, B_s>2, but this requirement does not apply if the lattices are different. In each series, distribution constants for the equilibria were also determined. Where possible, the calculated activities of the salts or the Gibbs excess energies of the solid solutions were compared with values reported by others who determined them by other methods. All the salt pairs studied show slight or strong positive deviations from ideality.     

也论化学元素周期表的形成和发展

In the time order, the author proposes that the discovery and development of the periodic table of chemical elements are divided into four stages:point→1D→2D→3D. This article cites the main historical facts and documents available to unscramble the above four stages, which will facilitate the teaching and scientific research of the periodic table.     

有机同系物性质的递变规律研究

以有机同系物结构重复单元数值连续变化为模型,得到同系物行质递变的两个基本规律：P=a+bn和P=c+kln(n+a/n+b),a,b,c,k均为常数,n为结构重复单元数值,P为同系物的物性。一般地,加和型性能遵守直线变化规律,而结构型和凝聚型性能遵守同系对数线性规律。