The possibility of regime changing in chain reactions with degenerate branching under the influence of external magnetic field

A reaction of hydrocarbons oxidation in the liquid phase is treated theoretically. The reaction system under discussion is a flow reactor, to the inlet of which the hydrocarbon is constantly delivered in the mixture with an inhibitor under oxygen saturation conditions; the reaction mixture constantly flows from the chamber at the same rate. The reaction gives rise to radicals that can subsequently recombine. It is shown that under certain conditions in this reaction system, three steady states may arise, two of which are stable and the third state is unstable. By varying rate constants of radical reactions by means of an external magnetic field, one can disturb the steady state stability and transfer the system to another steady state, which will be accompanied by an abrupt change in the concentration of reacting substances.     

Seven competing ways to recover the Michaelis–Menten equation reveal the alternative approaches to steady state modeling

The Michaelis–Menten enzymatic reaction is sufficient to perceive many subtleties of network modeling, including the concentration and time scales separations, the formal equivalence between bulk phase and single-molecule approaches, or the relationships between single-cycle transient probabilities and steady state rates. Seven methods proposed by different authors and yielding the same famous Michaelis–Menten equation, are selected here to illustrate the kinetic and probabilistic use of rate constants and to review basic techniques for handling them. Finally, the general rate of an ordered multistep reaction, of which the Michaelis–Menten reaction is a particular case, is deduced from a Markovian approach.     

Formamide as an organic modifier in MEKC with SDS

The effect of formamide (FA) as a modifier on the retention in MEKC with SDS as the detergent was investigated. The mobility of a series of alkylphenones and of a zwitterionic fluorescent compound as a function of the FA and the SDS concentration was determined for this purpose. Buffering electrolyte was borate, pH 9.23, with total ionic strength of 50 mM. The dependence of the mobility on the FA content – up to 63% w/w – of the BGE (at 10 mM SDS) allows the conclusion that the micelles are destabilized, and the CMC is shifted to higher values. In the system containing 33% FA or more no micelles are present anymore, and the retention factors of all compounds tend to zero. In an MEKC system with 27% v/v FA the CMC of SDS is increased from 2.4 mM in the aqueous BGE with the same buffer composition to 9.7 mM, a behavior that is in contrast to electrolyte‐free FA–water systems. The partition constants of free analytes and the formation constants of the adduct between analyte and detergent monomer (assuming 1:1 stoichiometry) were derived from the dependence of the mobility on the SDS concentration. In addition, the involved equilibria were extended by that from the distribution of the analyte–monomer adduct between aqueous and micellar phase, and the according partition constants were derived as well. A selective change in the extent of partitioning was observed for the zwitterionic compound. In general, all binding constants were decreased upon addition of FA, though to a different extent. Although the binding constants of the analyte–monomer associate were only slightly influenced, the most pronounced decrease is found for their partitioning into the micelles.     

Reversed-phase high-performance liquid chromatography of ionogenic compounds: comparison of retention models

Two kinds of retention models describing a behaviour of ionogenic substances in reversed-phase chromatographic systems were compared. Model A utilises a concept of limiting retention factors and is especially suitable for the prediction of retention of compounds co-existing in several forms in mobile phase. An effect of the concentration of organic modifier (e.g., methanol) on the magnitudes of the limiting retention factors and equilibrium constants (dissociation constants of the separated substances) can be expressed with the aid of various, more or less sophisticated, relationships. A stoichiometric displacement model (model B) in its original form simply relates the analyte retention to the content of organic modifier in the mobile phase. In this work, it was modified to also express an effect of the mobile phase pH introducing side equilibria (acid-base) into the model. Both models predict a sigmoidal dependence of the analyte retention factor on the mobile phase pH in accordance with experimental data, and allow, among others, to estimate dissociation constants from those data. Experimental dependencies between the analyte retention and the concentration of methanol in the mobile phase comply well with model A, whereas the stoichiometric displacement model could be used only in a limited range of the methanol concentrations.     

The thermodynamics of extraction equilibria

A simple graphical method for determination of thermodynamic equilibrium constants, developed for ion-exchange and solvent extraction processes, was successfully applied to a liquid exchangersystem. Close values of the thermodynamic equilibrium constants for the system uranyl chloride—hydrochloric acid—di-2-ethylhyxyl phosphoric acid—toluene (K=7.8±0.8) were obtained when the ionic strength of the aqueous phase was varied and the concentration of di-2-ethylhexyl phosphoric acid in the organic phase was kept constant, and vice versa.     

论化学反应动力学中的稳态假设

对单分子气相反应undemann机理提出了一个不用稳态假设的动力学新表述，并指出经典表述中的稳态假设是主观硬性加上的，缺少了一个条件。当反应气体压强变小时，经典表述中虽然应用稳态假设，但实际上是高活性中间产物的近似，并不真正存在稳态。稳态假设的适用性有两种不同的近似本质，一是平衡态近似或真稳态，另一是高活性中间产物近似，应予分辨。过去文献中往往把两者混在一起，这会导致得不到一般性结论，或所得一般性结论会有错误。文中也讨论了在复杂反应中真稳态的存在，而平衡态和真稳态的建立，都需经过一个初期瞬间过程，而高活性中间产物近似没有初期瞬间过程，因为不是一个形成稳态的过程。     

A kinetic study on the conversion of cis-2-butene with deuterium on a Pd/Fe3O4 model catalyst

The conversion of cis-2-butene with deuterium over a well-defined Pd/Fe(3)O(4) model catalyst was studied by isothermal pulsed molecular beam (MB) experiments under ultra high vacuum conditions. This study focuses on the processes related to dissociative hydrogen adsorption and diffusion into the subsurface of Pd nanoparticles and their influence on the activity and selectivity toward competing cis-trans isomerization and hydrogenation pathways. The reactivity was studied both under steady state conditions and in the transient regime, in which the reaction takes place on a D-saturated catalyst, over a large range of reactant pressures and reaction temperatures. We show that large olefin coverages negatively affect the abundance of D species, as indicated by a reduction of both reaction rates under steady state conditions as compared to the transient reactivity on the catalyst pre-saturated with D(2). Limitations in D availability during the steady state lead to a very weak dependence of both reaction rates on the olefin pressure. In contrast, when the surface is initially saturated with D, the transient reaction rates of both pathways exhibit positive kinetic orders on the butene pressure. Cis-trans isomerization and hydrogenation show kinetic orders of +0.7 and +1.0 on the D(2) pressure, respectively. Increasing availability of D noticeably shifts the selectivity toward hydrogenation. These observations together with the analysis of the transient reaction behavior suggest that the activity and selectivity of the catalyst is strongly controlled by its ability to build up and maintain a sufficiently high concentration of D species under reaction conditions. The temperature dependence of the reaction rates indicates that higher activation energies are required for the hydrogenation pathway than for the cis-trans isomerization pathway, implying that different rate limiting steps are involved in the competing reactions.     

The ternary system propyl propanoate+ hexane+chlorobenzene at 298.15 k

Differential thermal analysis shows many interesting properties that allow for prompt finding the place (p,T) and characteristics (endothermic, exothermic) of a phase transition or chemical reaction. In application to reactive sintering under active gas atmosphere at high pressure despite of numerous technical problems encountered during DTA measurements we found its unique possibilities. That allows for quantitative estimation of nitrogen involved in reaction of phase transition from the hexagonal phase to the cubic phase of MoN, and vice versa, in high gas pressure condition. DTA high gas pressure measurement system has the maximum operate temperature 2000°Cat pressure 2 GPa. This revised version was published online in August 2006 with corrections to the Cover Date.     

Pattern formation in excitable media with concentration-dependent diffusivities

We study a model of pattern formation in an excitable medium with concentration-dependent diffusivities. The reaction terms correspond to a two-variable Gray-Scott model in which the system has only one stable steady state. The diffusion coefficients of the two species are assumed to have a functional relationship with the concentration of the autocatalyst. A transition from self-replicating behavior to stationary spots is observed as the influence of the local autocatalyst concentration on the diffusion process increases. Notably, the transition occurs even though there is no change in the relative diffusivities of the activator and inhibitor. The observed time-independent patterns exhibit an unusual dependence on the size and geometry of an initial perturbation. Initial perturbations with a large spatial size, for example, sometimes revert to the homogeneous equilibrium state, whereas perturbations of smaller spatial extent develop into stable spots at the same parameter values.     

A New Formulation of the Lindemann Mechanism of Unimolecular Reactions

A new formulation of the Lindemann mechanism of unimolecular reactions in gaseous phase is presented, without the use of steady state hypothesis. It is hereby shown that the nature of applicability of steady state hypothesis in the regime of high reactant gas pressure is different from that in the regime of low gas pressure. In the former case it is an equilibrium approximation, while in the latter case it is a highly reactive intermediate approximation in no connection with a steady state. Furthermore for the latter case it is shown that in the classical formulation of Lindemann mecbRnism the use of steady state hypothesis is an ad hoc assumption. A highly reactive intermediate in the sense that its concentration is very small during the whole course of reaction is a necessary condition for the applicability of very reactive intermediate approximation. When the two distinctive nature of the applicability of steady state hypothesis is mlxed-up, wrong or useless conclusion may be arrived at. The only possible case of realizing a true steady state in a complex reaction is pointed out.     

Modeling and simulation of stationary catalytic processes

Generalized models for steady state catalytic processes are presented in matrix form. Multistep reaction rate control is assumed. Numerical algorithms for solving of the created linear and nonlinear equation systems are developed and tested. Four examples are considered: an Eley–Rideal-mechanism, a Langmuir–Hinshelwood mechanism, a dual route, dual site mechanism, and a monomolecular decomposition with steady state multiplicity. The overall reaction rates are simulated as a function of the reactant concentrations. A maximum reaction rate is obtained in the case of a Langmuir–Hinshelwood mechanism (example 2), the location of the rate maximum in the concentration domain is shifted towards the concentration of the reactant with the lowest adsorption constants. An Eley–Rideal mechanism (example 1) has always monotonously increasing rate curves. In the case of steady state multiplicity (example 4) all steady states could be simulated with the proposed algorithm. The computation of reaction rate surfaces is important in investigating the behavior of complicated catalytic systems (e.g., systems with multistep rate control and/or steady state multiplicity), in planning of experiments and in chemical reactor simulation.     

Role of the organic solvent modifier in the reversed phase high-performance liquid chromatography of polypeptides

Summary The retention behaviour of several polypeptide hormones on Bondapak C₁₈ columns has been examined using mobile phases of different acetonitrile percentage compositions containing 15 mM triethylammonium phosphate or 15 mM orthophosphoric acid buffers. Under these elution conditions, the capacity factors and the selectivity parameters of these polypeptide hormones show pronounced dependencies on the volume fraction of the organic solvent modifier. In the range 0–40% acetonitrile, the capacity factors were monotonously attenuated with increasing modifier percentages with the elution order essentially in accord with that hat anticipated for a reversed phase separation mode. At higher concentrations of acetonitrile, retention of the polypeptides to the octadecylsilica support progressively increased with elution order reversals indicative of a normal- or polarphase separation mode. These observations are discussed in terms of the interplay of hydrophobic and silanophilic interactions which occur between the ionised polypeptides and the stationary phase under these changing mobile phase conditions.High Performance Liquid Chromatography of Amino Acids, Peptides and Proteins, XXXII. For previous publication see ref. [1].     

A comparative potentiostatic study of the electrocrystallization of PbO2 on platinum and glassy carbon electrodes

The deposition of PbO₂ on platinum and glassy carbon electrodes was investigated experimentally. The comparison of the different behaviour on the two types of electrodes is presented. The effects of variation of temperature, potential, nucleation order and induction time-lags on the electrocrystallisation process are discussed.The present investigations have confirmed that electrocrystallisation of PbO₂ occurs through 3-D nucleation and growth on glassy carbon and most probably also on platinum. The data on platinum contains considerable noise from simultaneous chemical processes and is not amenable for analysis in a simple way. The steady state behaviour is unusual because it has generally been assumed that charge transfer is rate determining under most conditions. However, as shown here, if lattice incorporation is slow even at the steady state, it provides a method for separating the activation energies associated with the nucleation and growth rate constants. Finally, the dissolution of PbO₂ into the platinum substrate and its implication on transient rates merits more attention. In this context the Pt-PbO₂ system is probably not a good choice because of the large contribution of substrate oxidation to the measured transient rates.     

Variations of particle size and bed voidage distributions in expanded bed during transient operation processes

Changes in bed expansion are frequently encountered during an expanded bed adsorption, such as during the initial bed expansion, feed loading and washing processes. We have here studied the changes of local particle size distribution and bed voidage of an expanded bed in the initial bed expansion process as well as those during the changes in mobile phase viscosity, which imitated feed loading and column washing processes. Using a glass column modified with three side sampling ports and Streamline AC as the solid phase, experimental measurements on a series of operation moments during the transient processes were carried out by sampling the particles from within the column at different axial positions. In the initial bed expansion process, the gradual formation of an axial classification from a settled bed to a stable expanded bed was first displayed. By changing the mobile phase from water to 10% (w/w) glycerol solution or vice versa, the variations in both the particle size distribution and bed voidage corresponding to the increase or decrease of the bed height caused by the changes of the mobile phase viscosity were examined as well. The transient changes of the local particle size distribution and bed voidage first occurred in the bed bottom and then progressed from bottom to top along the axial direction. However, the changes of bed voidage at different axial positions were not unidirectional. That is, by changing the mobile phase to the high-viscosity glycerol solution, a constant increase of the bed voidage was observed in the bed bottom, while a distinct decrease of the bed voidage before its increase was involved at the middle and top positions. This is ascribed to the compression effect caused by the upward movement of the lower part particles.     

Measuring the interfacial tension of polymers in the presence of an interfacial modifier: Migrating the modifier to the interface

Compared to the dynamic mixing process used in melt blending operations, most techniques for measuring the interfacial tension can be considered as virtually static. For this reason, in order to measure the interfacial tension of an A-B immiscible system in the presence of an interfacial modifier, the problem of migrating the modifier to the interface is a central issue. In this study, the influence of the addition of an interfacial modifier, a polyethylene copolymer ionomer, on the interfacial tension between two high-density polyethylenes and a polyamide is investigated. The breaking thread method is used and the interfacial tension is measured as a function of ionomer content. In order to enhance the likelihood of placing the modifier in closer proximity to the interface, various sample preparations are compared. In all cases, the interfacial tension significantly drops with increasing ionomer content and tends to a limiting value. It is shown, however, that the preparation of the system for the breaking thread experiment via coextrusion using a conical die brings the modifier in closest proximity to the interface. With this approach an additional 1.45 times reduction of the interfacial tension at 10% compatibilizer concentration (based on the mass of HDPE) is observed compared to the classical technique of preparation. Confirmation of this effect is demonstrated using X-ray photoelectron spectroscopy where analysis of the thread surface of the system prepared by coextrusion indicates a more than fourfold enrichment of interfacial modifier. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1947–1958, 1998     

Influence of the structure of the alcoholic modifier on the enantioselective separation of nadolol

The influence of the structure of the alcoholic modifier of the mobile phase on the liquid chromatographic separation of the optical isomers of nadolol on a Pirkle-type chiral stationary phase was investigated. The isomers were separated as their chiral 1-naphthylureides on a column consisting of 3,5-dinitrobenzoyl- -leucine covalently bound to 3-μm aminopropylsilica, using an eluent consisting of n-hexane modified with an alcohol. A number of straight-chain, branched and unsaturated alcohols with carbon numbers ranging from 1 to 8 were evaluated. The choice of alcohol influenced both retention and selectivity, with optimum stereoselectivity being observed for C₃. The alcoholic modifiers selectively affected the retention and resolution of the two pairs of enantiomers that constitute nadolol. Thus chromatograms displaying two, three or four peaks could be obtained, depending on which modifier was employed. The best separation of all four isomers was achieved with ethanol as the modifier.     

Contributions on the Properties of Titanates with Ilmenite Structure. IV. The effect of an order-disorder transition on the high temperature electrical conductivity of NiTiO3

NiTiO₃ shows an order-disorder transition from an ordered ilmenite structure to a corundum structure at high temperatures. The transition is followed by a strong increase of the specific electrical conductivity. The conductivity was investigated as a function of temperature and oxygen activity. An order parameter according to common phase transition theories can be used to describe the behaviour of the conductivity in the transition region and vice versa. A model for the defect structure of NiTiO₃ is presented.     

Structure and charge-state dependence of the gas-phase ionization energy of proteins

Photoionization of protein ions: The ionization energy of polyprotonated protein cations in the gas phase measured using VUV synchrotron radiation appears to be correlated with the charge state z of the protein and its tertiary structure. A simple electrostatic model accounts for the results and also shows predictive capabilities to derive a mean radius R(m) of the protein ion from the ionization energy, and vice versa.     

Ce~(4+)/Ce~(3+)氧化还原体系线性极化与交流阻抗研究

用线性极化法和交流阻抗法研究了新型Ce~(4+)/Ce~(3+)-V~(2+)/V~(3+)氧化 还原电池中Ce~(4+)/Ce~(3+)半电池在不同Ce~(4+)浓度下的电化学行为。得出Ce~ (4+)浓度为0.2 mol/L时,其极化电阻最小,似为理论最佳浓度。实际应用需综合 考虑电池的库仓效率和能量效率等因素,还应尽可能选择较高浓度。测得不同浓度 下的阻抗参数表明,在Ce(SO_4)_2体系处于稳态时,不论是慢扫还是使用低的动频 率,Ce~(4+)的反应都为传质控制;而在体系处于暂态时,则不论是快扫还是使用 高扰动频率,都为传荷控制;而当体系介于稳态和暂态之间时,则为传质和传荷的 混合控制。因而可通过提高传质速率和加入电化学催化剂的方法来提高Ce~(4+) /Ce~(3+)体系的反应速率。     

Effects of Electrolytes on Manipulation of the Stationary Phase in Electrochemically Modulated Liquid Chromatography

Abstract

Electrolytes were found to have an important influence on the cell constant in electrochemically modulated liquid chromatography. The dependence of cell constant on electrolyte type did not reflect any relation with regard to electrolyte conductivity values. However, electrolytic species of larger ionic sizes result in significantly lower cell constants, and vice versa. It was also found that the cell constant is exponentially dependent on electrolyte concentration, with higher electrolyte concentrations resulting in decreased cell constants. When a potential ramp is applied to the working electrode, a steep change in the potential of the working electrode towards the final potential takes place directly after the application of the potential ramp. The change in the potential of the working electrode then follows an exponential decay isotherm, which depends on both electrolyte type and concentration.