Flow-reversal flow injection analysis-II Determination of glucose with a double-pump system

A new type of flow-injection procedure is proposed in which the samples are reversely pumped to the detector. In this procedure the injected samples are pumped into the reaction loop of a 6-way valve, then the valve is rotated to reverse the flow and the sample/reagent plug is pumped to the detector by another pump. The dispersion of the sample zone is low and the consumption of the reagent is very small. Therefore, its analytical potential for analysis with expensive reagents or long reaction times is high. The procedure has been applied to the determination of glucose in serum with an enzyme kit.     

Kinetics of a second order reaction involving two intermediate second order reactions

We have studied the kinetics of a reaction in which starting materials A and B react to form the products C and D directly, as well as by way of two additional intermediate reactions. In the first intermediate reaction, A and C react to form D and E, and in the second intermediate reaction, B and E react to form 2C. There are three conservation laws, which effectively reduce the number of variables to two, resulting in nonlinear coupled first order differential equations for [A](t) and [B](t). These equations are readily solved by standard numerical procedures, for various values of the relative reaction rates and starting concentrations. Our results are used to fit experimental data for the case in which A and B are 1-acetyl-4-(1-ethoxycarbonyl-1-cyano)methylene-1,4-dihydroquinoline and water, for which the first and third reverse reactions can be neglected.     

Transport phenomena in flow injection analysis without chemical reaction

Dispersion phenomena play a very important role in flow injection analysis. In this paper, physical transport phenomena in flow injection methods are discussed. Three different types of reactor — a straight tube, a helically coiled tube and a new single bead string reactor — are compared. Under similar flow conditions, the dispersion in the single bead string reactor is the lowest. The specific advantages of single bead string reactors are their very simple preparation and maintenance and the good reproducibility of the peaks. It is shown that in open capillary tubes (coiled or not) the Taylor dispersion equation is of very limited use, because the residence times are too short, and because secondary flow occurs in the case of coiled tubes.     

Flow injection analysis of ketoprofen based on the order transform second chemiluminescence reaction

This paper explores an order-transform-second-chemiluminescence (OTSCL) method combining the flow injection technique for the determination of ketoprofen. When ketoprofen solution was injected into the mixture after the end of the reaction of alkaline luminol and sodium periodate or sodium periodate solution was injected into the reaction mixture of ketoprofen and alkaline luminol, a new chemiluminescence (CL) reaction was initiated and strong CL signal was detected. A mechanism for the OTSCL has been proposed on the basis of the chemiluminescence kinetic characteristic, UV-visible absorption and chemiluminescent spectra. Under optimal experimental conditions, the CL response is proportional to the concentration of ketoprofen over the range of 2.0×10(-7) to 1.0×10(-5)mol/L with a correlation coefficient of 0.9950 and a detection limit of 8.0×10(-9)mol/L (3σ). The relative standard deviation for 11 repetitive determinations of 1.0×10(-6)mol/L ketoprofen is 2.9%. The utility of this method was demonstrated by determining ketoprofen in pharmaceutical formulations without interference from its potential impurities.     

The effect of gas injection on a thermal argon plasma flow in a water-cooled tube

The effect of gas injection on an atmospheric thermal argon plasma flow in a water-cooled tube was investigated experimentally and numerically. The injection gas is argon, helium, or nitrogen. The static pressure with helium injection increases greatly because of its high thermal conductivity, while little increase occurs for nitrogen injection because of the dissociation. The increasing rate of the static pressure depends on the ratio of the momentum term to the viscosity term. The heat flux to the tube wall with gas injection changes less than that without injection. The numerical results showed variations similar to the experimental ones.     

Mass transfer with a chemical reaction of the first order. Effect of axial diffusion

The role of diffusion in the direction of convection transport, which is usually neglected in mass (heat) transfer problems, is systematically investigated. Analytical solutions and asymptotic expressions are derived for cases of mass transfer coupled with a homogeneous and heterogeneous irreversible chemical reaction of the first order in plug flow, in Couette flow and in Couette flow with a moving interface. Irrespective of the flow situation, the effect of axial diffusion is of importance for small transformed distances in the direction of the convective transport. Then, the local mass transfer co-efficient is a square of the coefficient which is evaluated without the axial diffusion term. As expected, with an increase in the transformed distance both mass transfer coefficients tend to the same value. In the case of heterogeneous (surface) chemical reactions of the first order, the diffusion in the direction of convective transport is of minor importance. The same is observed when the case of simultaneous homogeneous and heterogeneous chemical reactions of the first order in uniform flow is considered.     

Micellar catalysis in flow injection systems: the nitrosation reaction.

The use of aqueous micellar carrier streams in flow injection is shown to catalyse on-line reactions and thereby improve the sensitivity relative to non-micellar systems. The effect of several different micellar systems on the nitrosation reaction of N,N-diethylaniline in acidic solution was investigated. The mechanism of the micellar enhancement is discussed and the sensitivities of the method in both aqueous and micellar media are compared. The presence of the cationic surfactant, cetyltrimethylammonium bromide, is shown to improve the sensitivity of the analysis. The effect of the micellar solution on the dispersion characteristics of the system was also studied. The greater viscosity of the micellar phase increases dispersion for non-reacting systems, but when monitoring a reaction product the increased reaction rate can counteract this and the micellar carrier can show less over-all dispersion than the aqueous carrier.     

化学反应处理的计算模型

介绍了一种将同类反应上升为合成反应知识和在计算机上实现反合成分析的方法,反合成分析是合成设计中最关键的一步,在本工作中采用了基于谋略键寻找的合成设计方法。它有逻辑宜于在计算机上实现的优点。为了实现这个方法,我们首次提出了一种能中肯地描述合成反应的计算模型—反应知识的分类模型。这一模型由三条规则定义：规则A-反应类型;规则B-发生反应的外部条件;规则C-不适宜采用这个反应的情况;这种计算模型能够将海量反应数据中最重要最基本的信息提炼出来,转换成计算机能处理的知识。它也包含有反应适用范围的信息,从而提高了析分过程的外推能力。     

On the chemical reaction of matter with antimatter.

A chemical reaction between the building block antiatomic nucleus, the antiproton (p or H- in chemical notation), and the hydrogen molecular ion (H2+) has been observed by the ATHENA collaboration at CERN. The charged pair interact via the long-range Coulomb force in the environment of a Penning trap which is purpose-built to observe antiproton interactions. The net result of the very low energy collision of the pair is the creation of an antiproton-proton bound state, known as protonium (Pn), together with the liberation of a hydrogen atom. The Pn is formed in a highly excited, metastable, state with a lifetime against annihilation of around 1 micros. Effects are observed related to the temperature of the H2+ prior to the interaction, and this is discussed herein.     

Temperature dependence of a first order diffusion-retarded chemical reaction in catalytically active membranes

A method is described to determine the activation energy of the intrinsic reaction rate constant of a diffusion-retarded first order chemical reaction in a catalytically active membrane from measurements of the temperature dependence of the apparent reaction rate constant. At the same time, the activation energy of the diffusion coefficient of substrate within the membrane phase is obtained. The method is tested by studying the hydrolysis of sucrose catalyzed by H⁺ counterions of a strong-acid cation exchange membrane.     

On the mathematical model of capillary electrophoresis

Summary The influence of the electroosmotic flow profile on the efficiency of capillary electrophoresis for a wide range of buffer concentrations and capillary diameters is studied. Thermal effects in the capillary, the finite size of solute molecules and their interactions with the capillary wall are also taken into consideration. The dependence of capillary electrophoresis efficiency and resolution on the zeta-potential values is investigated.Presented at the 19^th ISC, Aix-en-Provence, France, September 13–18, 1992.     

Stochastic simulation of chemical reaction by digital computer, I. The model

A stochastic model of complex chemical reactions is outlined. A discrete Markov process corresponds to the complex chemical reaction in the model i.e. the concentrations of the components are discrete quantities. The differences between the stochastic and deterministic models are discussed.

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Dispersion-convolution model for simulating peaks in a flow injection system

A dispersion-convolution model is proposed for simulating peak shapes in a single-line flow injection system. It is based on the assumption that an injected sample plug is expanded due to a "bulk" dispersion mechanism along the length coordinate, and that after traveling over a distance or a period of time, the sample zone will develop into a Gaussian-like distribution. This spatial pattern is further transformed to a temporal coordinate by a convolution process, and finally a temporal peak image is generated. The feasibility of the proposed model has been examined by experiments with various coil lengths, sample sizes and pumping rates. An empirical dispersion coefficient (D*) can be estimated by using the observed peak position, height and area (tp*, h* and At*) from a recorder. An empirical temporal shift (Phi*) can be further approximated by Phi*=D*/u2, which becomes an important parameter in the restoration of experimental peaks. Also, the dispersion coefficient can be expressed as a second-order polynomial function of the pumping rate Q, for which D*(Q)=delta0+delta1Q+delta2Q2. The optimal dispersion occurs at a pumping rate of Qopt=sqrt[delta0/delta2]. This explains the interesting "Nike-swoosh" relationship between the peak height and pumping rate. The excellent coherence of theoretical and experimental peak shapes confirms that the temporal distortion effect is the dominating reason to explain the peak asymmetry in flow injection analysis.     

On a diffusion model of a catalytic reaction

A model to describe a catalytic reaction with simultaneous diffusion is analyzed. The possibility of formation of periodic structures in space is shown.

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Force in SCF Theories. First and second derivatives of the potential energy hypersurface of chemical reaction systems

Accurate Hellmann–Feynman force method for the first and second derivatives of energy has been applied to the studies of the chemical reaction systems. We have studied (1) the electronic origins of the structure-reactivity correlations in the reactions CH₃ + H → CH₄ and CH₃ + CH₃ → C₂H₆ and (2) the geometries and force constants in the reaction intermediate and the transition state of the reactions F^? + HF → [FHF]^? → FH + F^? and H^? + CH₄ → CH₄ + H^?, respectively. An intuitive simplicity of the underlying concepts of the first and second derivatives of the present approach is shown in the analysis.     

On the application of open circuit relaxation spectroelectrochemistry to the diagnosis and evaluation of the kinetics of succeeding second order chemical reactions

The spectroelectrochemical technique of open circuit relaxation (OCR) has found limited application in the kinetic characterization of systems wherein the electrogenated absorbing species is consumed in a second or higher order reaction. This limited usage arises from the inapplicability of conventional homogeneous kinetic data analysis techniques to the absorbance-time transients observed in the OCR experiment. Treatment of such transients by conventional kinetic expressions (e.g., 1/A vs. t for second order reactions) results in non-linear plots which neither serve as diagnostic criteria for the assignment of kinetic order nor provide meaningful rate constants. This paper presents an empirical method for the treatment of spectroelectrochemical OCR data arising from post-electron transfer kinetic processes which exhibit second order dependence on the concentration of the electrogenerated absorbing species. This procedure, which takes into account the inhomogeneous distribution of the reactant species, affords reduced data plots which not only are linear, hence diagnostic of kinetic order, but also provide a valid measure of the bimolecular rate parameters characteristic of this type of dynamic system. The procedure has been applied to the treatment of OCR data for the reaction of 9,10-diphenylanthracene cation radical with 4-cyanopyridine in acetonitrile. Excellent agreement between the resulting kinetic parameters and those obtained using stopped-flow techniques has been demonstrated.     

The determination of chemical oxygen demand in waste-waters with dichromate by flow injection analysis

A simple method is described for the continuous determination of chemical oxygen demand (COD) in wastewater samples by flow injection analysis. Samples are injected into a water stream which merges with an acidic dichromate carrier solution. After reaction in a PTFE coil at 120°C, absorbances are measured at 445 nm. D-Glucose is satisfactory as a standard substance for COD in a variety of wastewaters. A sampling rate of 15 samples per hour can be achieved, and the detection limit and precision are 5 mg l^-1 as COD and 0.4%, respectively. Chloride concentrations of ? 100 mg l^-1 interfere slightly unless silver and/or mercury salts are added. COD values for various wastewater samples correlate well with those obtained by standard methods using dichromate or permanganate.     

Interference by neutron induced second order nuclear reaction in activation analysis of rare earths

In determining the trace impurities existing in high-purity rare earth samples by the neutron activation analysis, there are much interference due to nuclides induced from neutron induced second order nuclear reaction. This paper presents the degree of interference calculated over the ranges of irradiation time from 10⁵ to 10⁷ sec and of thermal-neutron flux from 1·10¹² to 1·10¹⁵ n·cm⁻²·sec⁻¹. According to the results of these calculations, degree of interference under the neutron irradiation condition for 288 hrs in the thermal-neutron flux of 3·10¹³n·cm⁻²·sec⁻¹ is concluded to be 6.4·10⁶ ppm Gd in Eu, 2.2·10⁴ ppm Sm in Eu, 1.9·10⁴ ppm Ho in Dy, 1.1·10³ ppm Eu in Sm, 1.1·10² ppm Ce in La and 1.1·10 ppm Tb in Gd, respectively. Especially, the Gd determination in the Eu target is extremely affected by¹⁵³Gd formed from the¹⁵¹Eu (n, γ) reaction. On the contrary, this reaction is effective in producing¹⁵³Gd activity.     

On the kinetics of styrene emulsion polymerization above CMC. I. A mathematical model

A detailed mathematical model of the kinetics of styrene emulsion polymerization has been proposed. Its main features/assumptions are compartmentalization, micellar and homogeneous nucleation, particle formation by both initiator‐derived and desorbed radicals, dependence on the particle size of the rate coefficients, thermodynamic considerations, and aqueous phase kinetics. The model predicts that micellar nucleation dominates over homogeneous nucleation and that the evolution of the nucleation rate reaches a maximum, where desorbed radicals have an important contribution. Initiator‐derived radicals with only one monomeric unit have also a significant contribution on the rate of capture in particles. The results suggest that the correctness of the instantaneous termination approach depends not only on the size of the particle, but also on the type of entering radical (initiator‐derived or monomeric). © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2201–2218, 2000