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本文计算的σ~△~E^H^O和σ△E^L^U值, 应用于苯系Ph(X)n六十多个分子的亲电或亲核反应活性比较, 结果同文献实验数据。σ~△~E^H^O值与分子间或分子内亲电反应活性呈正平行关系, 而σ~△~E^L^U值则正好相反, 但是CN、CF3和F取代基则例外。 相似文献
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稀土—丝氨酸配合物的热力学研究 总被引:3,自引:3,他引:3
在25℃和μ=0.15mol[NaCl]条件下,用电位法测定了L-丝氨酸的质子化常数、15个稀土元素与该配体生成配合物的稳定常数,表明稀土与L-丝氨酸可生成1:1及1:2配合物。讨论了“四分组效应”及钇的位置。用量热滴定法直接测定了稀土与L-丝氨酸生成1:1配合物的△H_(101)值,计算了△S_(101)和△G_(101)值。 相似文献
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指出了电化学反应中n值的非唯一确定性,阐述了电化学反应的Gibbs自由能改变值△rGm与其可逆电池电动势E之间的非唯一对应关系。 相似文献
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关于氧化还原滴定可行性讨论 总被引:1,自引:0,他引:1
一、问题的提出从平衡的观点考虑,判断一氧化还原反应可否用于滴定分析法,是从化学计量点时反应进行的完全程度出发,用反应体系的log K′或△E~(0′)值大小来判断的。由于反应类型不同,为达到一定反应完全程度,对log K′或△E~(0′)值的要求也不同。现行分析化学教材一般只讨论对称氧化还原电对的反应, 相似文献
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炔雌醇,又名乙炔雌二醇(Ethinylestradiol,EE),是一种雌激素.本文采用了现代电化学分析方法系统研究了炔雌醇在玻碳电极上的电化学行为.实验表明炔雌醇在玻碳电极上的氧化是不可逆过程,在不同pH值介质中,在玻碳电极上都有一定的吸附性.实验研究了在不同pH值条件下炔雌醇的各种电化学性质,并寻找到在不同条件下的定量方法,对实际样品进行了测定. 相似文献
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可再生清洁能源的开发和利用对人类社会的可持续发展具有重要意义。 基于动电效应的纳米孔道能量转换系统将流体机械能转化为电能,有望应用于微型电源部件、自驱动纳米机器、微机电体系等领域,为清洁能源发电系统的开发提供了全新的选择。 纳米孔道中的机械能-电能转换过程涉及固体孔道与流体界面间的相互作用,合理设计孔道界面的微观结构,对其进行化学修饰及探讨界面间的相互作用,是提高能量转换效率和输出功率的关键。 近年来,随着纳米技术的迅猛发展及人们对界面物理化学的深入研究,纳米孔道结构和纳流体发电体系能被更精准地设计和集成。 本文主要介绍了基于动电效应的纳米孔道能量转换系统的基本概念,重点关注了纳米孔道中动电效应的最新研究进展,并对该领域进行了展望,为纳米孔道动电效应能量转换系统、纳米发电机、自驱动纳米机器、可穿戴器件等领域的进一步发展和应用提供参考。 相似文献
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Carrique F Ruiz-Reina E Arroyo FJ Delgado AV 《The journal of physical chemistry. B》2006,110(37):18313-18323
In this paper, a general electrokinetic theory for concentrated suspensions in salt-free media is derived. Our model predicts the electrical conductivity and the electrophoretic mobility of spherical particles in salt-free suspensions for arbitrary conditions regarding particle charge, volume fraction, counterion properties, and overlapping of double layers of adjacent particles. For brevity, hydrolysis effects and parasitic effects from dissolved carbon dioxide, which are present to some extent in more "realistic" salt-free suspensions, will not be addressed in this paper. These issues will be analyzed in a forthcoming extension. However, previous models are revised, and different sets of boundary conditions, frequently found in the literature, are extensively analyzed. Our results confirm the so-called counterion condensation effect and clearly display its influence on electrokinetic properties such as electrical conductivity and electrophoretic mobility for different theoretical conditions. We show that the electrophoretic mobility increases as particle charge increases for a given particle volume fraction until the charge region where counterion condensation takes place is attained, for the above-mentioned sets of boundary conditions. However, it decreases as particle volume fraction increases for a given particle charge. Instead, the electrical conductivity always increases with either particle charge for fixed particle volume fraction or volume fraction for fixed particle charge, whatever the set of boundary conditions previously referred. In addition, the influence of the electric permittivity of the particles on their electrokinetic properties in salt-free media is examined for those frames of boundary conditions. 相似文献
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A theoretical analysis is presented to determine the forces of interaction between an electrically charged cylindrical particle and a charged plane boundary wall when the particle translates parallel to the wall and rotates around its axis in a symmetric electrolyte solution at rest. The electroviscous effects, arising from the coupling between the electrical and hydrodynamic equations, are determined as a solution of three partial differential equations, derived from R.G. Cox's general theory [J. Fluid Mech. 338 (1997) 1], for electroviscous ion concentration, electroviscous potential, and electroviscous flow field. It is assumed a priori that the double layer thickness surrounding each charged surface is much smaller than the length scale of the problem. Using the matched asymptotic expansion technique, the electroviscous forces experienced by the cylinder are explicitly determined analytically for small particle-wall distances for low and intermediate Peclet numbers. It is found that the tangential force usually increases the drag above the purely hydrodynamic drag, although for certain conditions the drag can be reduced. Similarly the normal force is usually repulsive, i.e., it is an electrokinetic lift force, but under certain conditions the normal force can be attractive. 相似文献
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Labbez C Jönsson B Pochard I Nonat A Cabane B 《The journal of physical chemistry. B》2006,110(18):9219-9230
In this paper, we are concerned with the charging and electrokinetic behavior of colloidal particles exhibiting a high surface charge in the alkaline pH range. For such particles, a theoretical approach has been developed in the framework of the primitive model. The charging and electrokinetic behavior of the particles are determined by the use of a Monte Carlo simulation in a grand canonical ensemble and compared with those obtained through the mean field theory. One of the most common colloidal particles has been chosen to test our theoretical approach. That is calcium silicate hydrate (C-S-H) which is the main component of hydrated cement and is known for being responsible for cement cohesion partly due to its unusually high surface charge density. Various experimental techniques have been used to determine its surface charge and electrokinetic potential. The experimental and simulated results are in excellent agreement over a wide range of electrostatic coupling, from a weakly charged surface in contact with a reservoir containing monovalent ions to a highly charged one in contact with a reservoir with divalent ions. The electrophoretic measurements show a charge reversal of the C-S-H particles at high pH and/or high calcium concentration in excellent agreement with simulation predictions. Finally, both simulation and experimental results clearly demonstrate that the mean field theory fails not only quantitatively but also qualitatively to describe a C-S-H dispersion under realistic conditions. 相似文献
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Ohshima H 《Colloids and surfaces. B, Biointerfaces》2004,38(3-4):139-141
A theory of electroosmosis in an array of parallel soft cylinders (i.e. polyelectrolyte-coated cylinders) in a salt-free medium is presented. It is shown that there is a certain critical value of the particle charge and that if the particle charge is greater than the critical value, then the electroosmotic velocity becomes constant independent of the particle charge due to the counterion condensation effects, as in the case of other electrokinetic phenomena in salt-free media. 相似文献
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Hanieh Hadady Fereshteh Karamali Fatemeh Ejeian Shaghayegh Haghjooy Javanmard Laleh Rafiee Mohammad Hossein Nasr Esfahani 《Electrophoresis》2021,42(20):2018-2026
Extracellular vesicles (EVs) are cell-derived nanoscale vesicles involved in intracellular communication and the transportation of biomarkers. EVs released by mesenchymal stem cells have been recently reported to play a role in cell-free therapy of many diseases. However, the demand for better research tools to replace the tedious conventional methods used to study EVs is getting stronger. EVs' manipulation using alternating current (AC) electrokinetic forces in a microfluidic device has appeared to be a reliable and sensitive diagnosis and trapping technique. Given that different AC electrokinetic forces may contribute to the overall motion of particles and fluids in a microfluidic device, EVs' electrokinetic trapping must be examined considering all dominant forces involved depending on the experimental conditions. In this paper, AC electrokinetic trapping of EVs using an interdigitated electrode arrays is investigated. A 2D numerical simulation incorporating the two significant AC electrokinetic phenomena (Dielectrophoresis and AC electroosmosis) has been performed. Theoretical predictions are then compared with experimental results and allow for a plausible explanation of observations inconsistent with DEP theory. It is demonstrated that the inconsistencies can be attributed to a significant extent to the contribution of the AC electroosmotic effect. 相似文献
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The main theme of the present work is to investigate the electrokinetic effects on liquid flow and heat transfer in a flat microchannel of two parallel plates under asymmetric boundary conditions including wall-sliding motion, unequal zeta potentials, and unequal heat fluxes on two walls. Based on the Debye-Huckel approximation, an electrical potential solution to the linearized Poisson-Boltzmann equation is obtained and employed in the analysis. The analytic solutions of the electrical potential, velocity distributions, streaming potential, friction coefficient, temperature distribution, and heat transfer rate are obtained, and thereby the effects of electrokinetic separation distance (K), zeta-potential level (zeta;(1)), ratio of two zeta potentials (r(zeta) identical with zeta;(2)/zeta;(1)), wall-sliding velocity (u(w)), and heat flux ratio (r(q) identical with q"(2)/q"(1)) are investigated. The present results reveal the effects of wall-sliding and zeta-potential ratio on the hydrodynamic nature of microchannel flow, and they are used to provide physical interpretations for the resultant electrokinetic effects and the underlying electro-hydrodynamic interaction mechanisms. In the final part the results of potential and velocity fields are applied in solving the energy equation. The temperature distributions and heat transfer characteristics under the asymmetrical kinematic, electric, and thermal boundary conditions considered presently are dealt with. 相似文献
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Electrokinetic motion of a micro oil droplet beneath a glass slide was experimentally investigated in this paper. The micro oil droplets were released under the glass slide in an aqueous solution and the motion along the glass slide was measured by a microscope. The experimental results indicate that while the electrokinetic mobility increases with the applied electric field, it decreases with the oil droplet size and the ionic concentration of the aqueous solution, respectively. By changing the zeta potential of the glass‐liquid interface using polybrene coating from negative to positive, the direction of the electrokinetic mobility is reversed and the absolute value of the electrokinetic mobility increases significantly. Finally, pH effects were also investigated, and it was found that the electrokinetic mobility of the droplets reaches a maximum at pH = 6~8. 相似文献
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The electrophoretic mobility of silica nanospheres was shown to be a function of separation conditions such as pH and phosphate concentration of a carrier electrolyte. The separation selectivity can be controlled by the separation conditions and optimised depending on the sample composition. The effects of pH and phosphate concentration of buffer solutions on the nanosphere electrophoretic mobility are explained using the Overbeek-Booth electrokinetic theory taking into account both electrophoretic retardation and the relaxation effect. 相似文献
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Duval JF 《Journal of colloid and interface science》2004,269(1):211-223
Double layers (DL) at amphifunctionally electrified interfaces, such as that of an oxidized metal in an aqueous electrolyte solution, arise from coupling between ionic and electronic surface-charging processes. The electronic component enters the double-layer formation in the well-known situation where a potential is externally applied. In that case, the DL is fully or partly polarized depending on the possibility of interfacial electron transfer, that is, a faradaic process. This paper reports on the conjunction of the chemical/electrochemical processes at the interface in the case where the solution contains a redox-active couple. This makes it possible to polarize/depolarize a DL without invoking any external circuit. Streaming potential data obtained for the gold/(Fe(CN)6(3-)/Fe(CN)6(4-), KNO3) electrolyte interface are analyzed in terms of a recently developed theory which takes into account reversible bipolar faradaic depolarization, the inherent nonlinearity of the lateral field, and the effects of flow on the rate of the faradaic reactions. It appears that the theory largely overestimates the bipolar currents, leading to physically unrealistic zeta-potentials. A careful analysis of monopolar voltammetric data reveals quasi-reversible behavior of the redox couple under the typical convective conditions and electrolyte compositions met in electrokinetic experiments. Inclusion of reduced reversibility (the extent of which is position-dependent under the streaming-potential measurement conditions) leads to a consistent set of zeta-potentials which compare well to the values for the background electrolyte. 相似文献