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131.
Michael K. -H. Kiessling 《Journal of statistical physics》1990,59(5-6):1157-1186
The canonical equilibrium measure of classical two-component Coulomb matter with regularized interactions is analyzed in a finite volume. It is shown that, in the mean-field regime, the one-particle density is inhomogeneous on a new characteristic length scale inh. For a system ofN positive andN negative particles, inh and the characteristic length scale of correlations corr (=Debye screening length) are related via inh=(2N)1/2 corr. The major conceptual conclusion that is drawn from this is that one needs two nontrivial complementary thermodynamic limits to define the equilibrium thermodynamics of two-component Coulomb systems. One of them is the standard thermodynamic limit (infinite volume), where one takesN, corr fixed. Its complementary limit is characterized byN, inh fixed, and is a finite-volume inhomogeneous mean-field limit. The most prominent new feature in the mean-field thermodynamic limit, which is absent in the standard thermodynamic limit, is an anomalous first-order phase transition where the Coulomb system explodes or implodes, respectively. The phase transition is connected with the existence of a metastable plasma phase far below the ionization temperature. 相似文献
132.
For an exactly soluble classical spin model with long-range inhomogeneous coupling it is proved that in the absence of external magnetic field the free energy is aC
function of the temperature at the critical point. 相似文献
133.
P. J. Forrester 《Journal of statistical physics》1988,51(3-4):457-479
The Coulomb system consisting of an equal number of positive and negative charged rods confined to a one-dimensional lattice is studied. The grand partition function can be calculated exactly at two values of the coupling constant=q
2/k
B
T (q denoting the magnitude of the charges). The exact results lead to the conjecture that in the complex scaled fugacity plane, all the zeros of the grand partition function lie on the negative real axis for<2, on the point=–1 for=2, and on the unit circle for>2. In addition, for>4, we conjecture in general and prove at=4 that the zeros pinch the real axis in the thermodynamic limit, with an essential singularity in the pressure at the reduced density 1/2. 相似文献
134.
Sahadev R. K. Sharma S. K. Sindhwani 《Monatshefte für Chemie / Chemical Monthly》1992,123(10):883-889
Summary The chelation behaviour of some trivalent lanthanide and yttrium metal ion with biologically active 2-hydroxy-1-naphthaldehyde thiosemicarbazone (HNATS) has been investigated by potentiomotric measurements at 20±0.5°C in 75% (v/v) dioxane-water medium at various ionic strengths of sodium perchlorate. The method of Bjerrum and Calvin, as modified by Irving and Rossotti has been used to find out the values of
(average number of ligand bound per metal ion) andpL (free ligand exponent). The formation constants of metal chelates have been computed on a PC-XT computer, using a program patterned after that of Sullivan et al. to give
n
values using weighted least squares method. TheS
min
values (S
min
=2) have been calculated. The order of formation constants of chelates was found to be: La3+3+3+3+3+3+3+3+3+3+. The formation constants of the chelates formed have been correlated to size and ionization potentials of the metal ions.
Potentiometrische Untersuchungen der Komplexierungsgleichgewichte zwischen einigen trivalenten Metallionen und biologisch aktivem 2-Hydroxy-1-naphthaldehyd-thiosemicarbazon (HNATS)
Zusammenfassung Es wurde das Chelierungsverhalten einiger trivalenter Lanthanidenionen mit biologisch aktivem 2-Hydroxy-1-naphthaldehyd-thiosemicarbazon (HNATS) mittels potentiometrischer Messungen bei 20±0.5°C in 75% (v/v) Dioxan-Wasser bei verschiedener Ionenstärke an Natriumperchlorat untersucht. Die Methode nach Bjerrum und Calvin in der Modifikation nach Irving und Rossotti wurde zur Ermittlung der Werte (mittlere Anzahl an Liganden pro Metallion) undpL (Exponent an freiem Liganden) verwendet. Die Komplexbildungskonstanten wurden in Anlehnung an Sullivan et al. an einem PC-XT Computer errechnet. DieS min-Werte (S min=2) wurden ebenfalls bestimmt. Die Reihung der Chelatbildungskonstanten war: La3+相似文献3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+. Die Bildungskonstanten sind mit der Größe und dem Ionisierungspotential der Metallionen zu korrelieren.
135.
Yuichiro Tada Masakatsu Ueno Noriaki Tsuchihashi Kiyoshi Shimizu 《Journal of solution chemistry》1992,21(9):971-985
The limiting molar conductances ° of deuterium chloride DCl in D2O were determined as a function of pressure and temperature in order to examine the proton-jump mechanism in detail. The excess deuteron conductances °E(D
+), as estimated by the equation [°E(D
+) = °(DCl/D
2
O) – °(KCl/D
2
O)], increases with an increase in the pressure and temperature as well as the excess proton conductance [°E(H
+) = °(HCl/H
2
O) – °(KCl/H
2
O)]. The isotope effect on the excess conductances, however, depends on the pressure and temperature contrary to the model proposed by Conway et al.: °E(H
+)/°E(D
+) decreases with increasing pressure and temperature. The magnitude of the decrease with pressure becomes more prominent at lower temperature. These results are discussed in terms of the pre-rotation of adjacent water molecules, the bending of hydrogen bonds with pressure, and the difference in strength of hydrogen bonds between D2O and H2O. 相似文献
136.
P. G. J. van Dongen 《Journal of statistical physics》1989,54(1-2):221-271
A general method is used for describing reaction-diffusion systems, namely van Kampen's method of compounding moments, to study the spatial fluctuations in reaction-limited aggregation processes. The general formalism used here and in subsequent publications is developed. Then a particular model is considered that is of special interest, since it describes the occurrence of a phase transition (gelation). The corresponding rate constants for the reaction between two clusters of sizei and sizej areK
ij=ij (i, j=1, 2,). For thediffusion constants D
j of clusters of sizej the following class of models is considered:D
j=D if 1Js andD
j=0 ifj>s. The casess= ands< are studied separately. For the models= the equal-time and the two-time correlation functions are calculated; this modelbreaks down at the gel point. The breakdown is characterized by a divergence of the density fluctuations, and is caused by the large mobility of large clusters. For all models withs< the density fluctuations remain finite att
c, and the equal-time correlation functions in the pre- and in the post-gel stage are calculated. Many explicit and asymptotic results are given. From the exact solution the upper critical dimension in this gelling model isd
c=2. 相似文献
137.
138.
139.
140.
Seven transition metal molybdovanadoarsenic heteropoly compounds have been synthesized and characterized using IR, UV, TG-DTA, pH potential titration techniques. The molecular formulae of these compounds are pro-posed to be HxMyAsMO10V2O40·zH2O(x=1~3, y=1,2, M=Cr, Mn, Fe, Co, Ni, Cu, Zn).They are all keggin structure. Surface nature of these compounds have been investigated by temperature programmed desorption and temperature programmed reduction techniques. NH3-TPD results show that in TPD profiles of the compounds there are two desorption peaks corresponding to weak acid sites of desorption, respectively. Desorbing activativon energy and preexponential factor of weak acid site of desorption for compounds have been calculated. H2-TPR re-sults show that introducting transtion metal to molybdovanarsenic acid, the reduction peak temperatures of H2-TPR shift regularly with increasing d electron numbers of transition metals. In addition, Zn and Cu heteropoly com-pounds have yet apparent effect of hydrogen spill over. 相似文献