Isotope effect in proton-transfer and association-dissociation reactions for butylamine by ultrasonic relaxation methods

Ultrasonic absorption coefficients were measured for butylamine in heavy water (D2O) in the frequency range from 0.8 to 220 MHz and at concentrations from 0.0278 to 2.5170 mol dm(-3) at 25 degrees C; two kinds of relaxation processes were observed. One was found in relatively dilute solutions (up to 0.5 mol dm(-3)), which was attributed to the hydrolysis of butylamine. In order to compare the results, absorption measurements were also carried out in light water (H2O). The rate and thermodynamic parameters were determined from the concentration dependence of the relaxation frequency and the maximum absorption per wavelength. The isotope effects on the diffusion-controlled reaction were estimated and the stability of the intermediate of the hydrolysis was considered while comparing it with the results for propylamine in H2O and D2O. Another relaxation process was observed at concentrations greater than 1 mol dm(-3) in D2O. In order to examine the solution characteristics, proton NMR measurements for butylamine were also carried out in D2O. The chemical shifts for the gamma- and delta-proton in butylamine molecule indicate the existence of an aggregate. From profiles of the concentration dependence of the relaxation frequency and the maximum absorption per wavelength of sound absorption, the source of the relaxation was attributed to an association-dissociation reaction, perhaps, associated with a hydrophobic interaction. The aggregation number, the forward and reverse rate constants and the standard volume change of the reaction were determined. It was concluded from a comparison with the results in H2O that the hydrophobic interaction of butylamine in D2O is stronger than that in H2O. Also, the isotope effect on this reaction was interpreted in terms of the solvent structure.

Specific mass spectrometric fragmentations from the dissociation of intermediate ion-neutral complexes

It is reported that two kinds of specific mass spectrometric fragmentations are generated from dissociations of the intermediates of both the ion-neutral complex and the proton-bound complex. Collision-induced dissociation, isotopic labelling, and semi-empirical AM1 calculations were used to investigate the formation mechanism of the ion of m/z 139 from ionized tetrahydroimidazole-substituted methylene beta-diketones and the unimolecular fragmentations pathway of 3-phenyl-1-butyn-3-ol upon electron impact.

UNIMOLECULAR DISSOCIATION REACTIONS OF DOUBLY-CHARGED IONS [C12H12N2O](2+) AND [C12H12N2S](2+) IN GAS-PHASE

The unimolecular dissociation reactions of doubly charged ions were reported, which resulted from a tandem mass spectrometer and a reversed geometry double focusing mass spectrometer by electron impact, Mass analyzed ion kinetic energy spectrometry (MIKES) was used to obtain the kinetic energy releases in charge separation reactions of doubly charged ions, The intercharge distances between the two charges at transition states can be calculated from the kinetic energy releases, Transition structures of unimolecular dissociation reactions were infered from MIKES and MS/MS.

THERMODYNAMICS OF AMINO-ACID DISSOCIATION IN MIXED-SOLVENTS .3. GLYCINE IN AQUEOUS GLUCOSE SOLUTIONS FROM 5-DEGREES-C TO 45-DEGREES-C

The first thermodynamic dissociation constants of glycine in 5, 15 mass % glucose + water mixed solvents at five temperatures from 5 to 45-degrees-C have been determined from precise emf measurements of a cell without liquid junction using hydrogen and Ag-AgCl electrodes and a new method of polynomial approximation proposed on the basis of Pitzer's electrolytic solution theory in our previous paper. The results obtained from both methods agree within experimental error. The standard free energy of transfer for HCl from water to aqueous mixed solvent have been calculated and the results are discussed.

Formation and dissociation of protonated pyridine-methanol cluster ions at 355 and 266 nm

The multi-photon ionization process of the hydrogen-bond cluster of pyridine-methanol has been investigated using a conventional and reflectron time-of-flight mass spectrometer (RTOF-MS) at 355 and 266 nm laser wavelengths, respectively. The sequences of the protonated cluster ions (CH3OH)(n)H+ and (C5H5Nn)(CH3OH)(m)H+ (n = 1,2) were observed at both laser wavelengths, while the sequence of the cluster ions (CH3)OHn (H2O)H+ was observed only at 355 nm laser wavelength. The difference between the relative signal intensities of the protonated methanol cluster ions at different laser wavelengths is attributed to different photoionization mechanisms. Some nascent cluster ions in metastable states dissociated during free flight to the detector. The dissociation kinetics is also discussed. (C) 2000 Elsevier Science B.V.

Determination of dissociation constants of Strychnos alkaloids from Strychnos nux-vomica L. by capillary electrophoresis

An accurate capillary electrophoresis method was developed for the determination of dissociation constants of five Strychnos alkaloids from Strychnos nux-vomica L. The method relies on measuring the effective mobility of the solute as a function of the buffer pH. The mathematical relationship was strictly derived from the fundamental electrophoresis theory and the dissociation equilibrium of a weak base without any simplifications. Careful optimization of the running buffer permitted base-line resolution of the five structurally similar alkaloids.

Covariance analysis of the Coulomb explosion of ammonia induced by intense nanosecond laser at 532 nm

The Coulomb explosion of ammonia clusters induced by nanosecond laser at 532 not with an intensity of similar to 10(12) Wcm(-2) has been studied by time of flight mass spectrometry. The dominant multiply charged ions are N3+ and N2+ with kinetic energies of 110 and 50 eV respectively. The electrons generated from the multiphoton ionization are heated through inverse bremsstrahlung by the laser field when colliding with neutral or ionic particles. When their energies surpass the corresponding ionization potentials of the molecules or ions, the subsequent electron impact ionization may take place thus resulting in multi-charged nitrogen ions. Covariance analysis is made to study the possible pathways of the Coulomb explosion.

Increasing Critical Sensitivity of the Load/Unload Response Ratio before Large Earthquakes with Identified Stress Acclumulation Pattern

The Load/Unload Response Ratio (LURR) method is proposed for short-to-intermediate-term earthquake prediction [Yin, X.C., Chen, X.Z., Song, Z.P., Yin, C., 1995. A New Approach to Earthquake Prediction — The Load/Unload Response Ratio (LURR) Theory, Pure Appl. Geophys., 145, 701–715]. This method is based on measuring the ratio between Benioff strains released during the time periods of loading and unloading, corresponding to the Coulomb Failure Stress change induced by Earth tides on optimally oriented faults. According to the method, the LURR time series usually climb to an anomalously high peak prior to occurrence of a large earthquake. Previous studies have indicated that the size of critical seismogenic region selected for LURR measurements has great influence on the evaluation of LURR. In this study, we replace the circular region usually adopted in LURR practice with an area within which the tectonic stress change would mostly affect the Coulomb stress on a potential seismogenic fault of a future event. The Coulomb stress change before a hypothetical earthquake is calculated based on a simple back-slip dislocation model of the event. This new algorithm, by combining the LURR method with our choice of identified area with increased Coulomb stress, is devised to improve the sensitivity of LURR to measure criticality of stress accumulation before a large earthquake. Retrospective tests of this algorithm on four large earthquakes occurred in California over the last two decades show remarkable enhancement of the LURR precursory anomalies. For some strong events of lesser magnitudes occurred in the same neighborhoods and during the same time periods, significant anomalies are found if circular areas are used, and are not found if increased Coulomb stress areas are used for LURR data selection. The unique feature of this algorithm may provide stronger constraints on forecasts of the size and location of future large events.

Comparison of the Dynamic Response of a Saturated Soil Between Two Models

By comparing the dynamic responses of saturated soil to Biot's and Yamamoto's models, the properties of the two models have be pointed out. First of all, an analysis has been made for energy loss of each model from the basic equations. Then the damping of elastic waves in coarse sand and fine sand with loading frequency and soil's parameters have been calculated and the representation of viscous friction and Coulomb friction in the two models has been concluded. Finally, the variations of loading wave damping and stress phase angles with water depth and soil's parameters have been obtained as loading waves range in ocean waves.

Comparison of existing poroelastic models for wave damping in a porous seabed

Mechanism of wave-seabed interaction has been extensively studied by coastal geotechnical engineers in recent years. Numerous poro-elastic models have been proposed to investigate the mechanism of wave propagation on a seabed in the past. The existing poro-elastic models include drained model, consolidation model, Coulomb-damping model, and full dynamic model. However, to date, the difference between the existing models is unclear. In this paper, the fully dynamic poro-elastic model for the wave-seabed interaction will be derived first. Then, the existing models will be reduced from the proposed fully dynamic model. Based on the numerical comparisons, the applicable range of each model is also clarified for the engineering practice.

Modification of Bertrand's theorem and extended Runge-Lenz vector

It is shown that for a particle with suitable angular moments in the screened Coulomb potential or isotropic harmonic potential, there still exist closed orbits rather than ellipse, characterized by the conserved aphelion and perihelion vectors, i.e. extended Runge-Lenz vector, which implies a higher dynamical symmetry than the geometrical symmetry O-3. The closeness of a planar orbit implies the radial and angular motional frequencies are commensurable.

经典轨道的封闭性和径向Schrodinger方程的因式分解

研究表明，保证经典轨道具有封闭性的Bertrand定理可以进一步推广，在适当的角动量睛，仍存在着非椭圆的闭合轨道。对于屏蔽Coulomb场，可获得广义Runge-Lenz矢量。这种轨道封闭性与径向Schrodinger方程因式分解相对应。

一种修正的莫尔-库仑本构模型及其应用

莫尔-库仑本构模型是理想弹塑性的，只考虑了强度随围压的变化，但没有考虑弹性模量随围压和应力水平的变化情况，这不符合地质材料的实际特性，借助于邓肯-张非线性弹性模型对切线模量的处理方法，对M-C模型中的弹性模量进行了修正。修正以后，弹性阶段的应力-应变曲线将表现为双曲线。为了将该修正模型写进FLAC^3D程序，特编制了前处理程序，并用来对刚性桩的横向承载力进行了数值分析。因为该模型没有对卸载模量重新定义，所以该模型较适合于持续加载的情况。

波浪、海洋土参数对海床稳定性影响

基于Yamamoto的多孔弹性介质模型，研究了波生底床的稳定性。通过给出的有限深底床下土响应分析解，针对三种土质底床，讨论了主要波参数和土参数对这些底床稳定性的影响。与其他土模型计算结果进行了比较，分析了海洋土内部Coulomb摩擦因素的影响。