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81.
In the past, few theoretical attempts have been made to describe quantitatively the adsorption of ionic surfactants at liquid
interfaces. Well-known adsorption isotherms due to Frumkin or Hill–de Boer cannot respond to the specific electrostatic and
geometric properties of the surfactant molecules. Our approach is based on a combination of the Gouy–Chapman theory with a
modified Frumkin isotherm. The modification implies that the system is free to choose an optimal head group area and an optimal
arrangement of the surfactant molecules in the interface as a function of bulk concentration. Interaction energies between
neighbouring adsorbed surfactant molecules and between surfactant and water molecules are taken into consideration. The minimum
of the Gibbs free energy of the system is equivalent to a minimal interfacial tension. Thus, the thermodynamically stable
isotherm can be obtained as the lower envelope of the family of σ versus ln c isotherms resulting from different choices of the model parameters, including the area per molecule. According to the Gibbs
equation, the Γ versus ln c adsorption isotherm is obtained as the derivative of this envelope. By variation of the model parameters, the envelope of
the calculated adsorption isotherms can be fitted to experimental data of the interfacial tension versus bulk concentration.
A computer program is used to calculate the σ versus c and the Γ versus ln c curves as well as to fit the parameters.
Received: 28 October 1999/Accepted: 8 February 2000 相似文献
82.
The acid-catalysed esterification of myristic acid with isopropanol was studied by using near-infrared spectroscopy (NIR) in combination with soft-modeling curve resolution (MCR) methodology with a view to establishing the effect of experimental variables on the reaction kinetics. The reaction was conducted at temperatures above the boiling point of the alcohol, with continuous addition of an isopropanol/water mixture to the reactor. Spectral and concentration profiles were determined by applying soft-modeling curve resolution methodology to a column-wise augmented data matrix containing the spectra for the pure components. MCR profiles were compared with reference values and found to depart from then by less than 3% as %RSE for concentrations and to exhibit correlation above 0.999 for spectra.The reaction kinetics as estimated from the concentration profiles was found to be pseudo-first-order. Also, the pseudo-first-order rate constant was found to depend on the flow-rate of the isopropanol/water mixture and its water content; although the constant decreased with increase in the proportion of water, a content of ca. 15% could be used without important retarding effects on the kinetics. The proposed NIR-MCR method allows the rate constant and the influence of the initial water content to be determined with a view to minimizing consumption of the raw materials and optimizing the experimental conditions. 相似文献
83.
Summary The elution behavior of alkali and earth alkaline cations has been studied on a newly synthesized weak cationexchanger (WCX). Applying this stationary phase isocratic separation of these cations is possible. The dependence of retention on competing ion concentration is described via a simple model. The influence of crown ethers as well as organic eluent additives on selectivity and peak efficiency is demonstrated. With optimized separation such cations can be determined with detection limits of about 0.5 ppm using a conductivity detector without ion suppression. 相似文献
84.
J. Zhu 《Mathematical Methods of Operations Research》1992,36(4):359-377
We present a primal-dual path following interior algorithm for a class of linearly constrained convex programming problems with non-negative decision variables. We introduce the definition of a Scaled Lipschitz Condition and show that if the objective function satisfies the Scaled Lipschitz Condition then, at each iteration, our algorithm reduces the duality gap by at least a factor of (1–/n), where is positive and depends on the curvature of the objective function, by means of solving a system of linear equations which requires no more than O(n3) arithmetic operations. The class of functions having the Scaled Lipschitz Condition includes linear, convex quadratic and entropy functions. 相似文献
85.
Summary A simple optimization method based on the well-known Rs-minimum method and on the information theory of FUMI Φ is proposed.
Resolution (Rs), peak area and height (or width) are the only parameters necessary for the calculation of the information
Φ and information flow ϑ. The most precise analysis can be selected as the chromatogram having maximal ϑ. Mobile phase composition,
column length, flow rate, detection wavelength, amount of internal standard, etc. can be optimized by this method. 相似文献
86.
Theoretical equations are given to relate resolution with development distance. Comparative experiments undertaken with quaternary ammonium compounds as test substances and using a selection of basic drugs are presented. As expected, resolution decreases with shorter development distance. However, this effect is less pronounced for compounds with small Rf values and when the spot size at the starting point is kept small. It was also shown that, for correctly assessing resolution in relation to development distance, the amounts of material spotted have to be decreased for shorter development distances. 相似文献
87.
The volumetric properties of two reservoir fluid samples collected from one condensate gas well and one natural gas well were measured under four groups of temperatures, respectively, with pressure up to 116 MPa. For the two samples examined, the experimental results show that the gas compressibility factor increases with the increase of pressure. But the influence of the temperature is related to the range of the experimental pressure. It approximately decreases with the increase of temperature when the pressure is larger than (45 to 50) MPa, while there is the opposite trend when the pressure is lower than (45 to 50) MPa. The dew point pressure was also determined for the condensate gas sample, which decreases with the increase of temperature. The capabilities of four empirical correlations and a thermodynamic model based on equation of state for describing gas compressibility factor of reservoir fluids under high pressure were investigated. The comparison results show that the thermodynamic model recommended is the most suitable for fluids whatever produced from high-pressure reservoirs or conventional mild-pressure reservoirs. 相似文献
88.
The longitudinal motions and vertical accelerations of a floating torus as well as wave motion inside the torus are studied by model tests in regular deep-water waves. Comparisons are made with linear and partly with second-order potential-flow theory for the smallest examined experimental wave height-to-wave length ratio 1/120. Reasonable agreement is obtained, in particular for the linear problem. The importance of 3D flow, hydroelasticity and strong hydrodynamic frequency dependency is documented. Experimental precision errors and bias errors, for instance, due to tank-wall interference are discussed. Numerical errors due to viscous effects are found to be secondary. Experiments show that the third and fourth harmonic accelerations of the torus matter and cannot be explained by a perturbation method with the wave steepness as a small parameter. 相似文献
89.
酚醛树脂是一种广泛使用的合成树脂,包括热固性和热塑性两类,具有良好的阻燃性、耐热性和耐腐蚀性。酚醛纤维是由酚醛树脂所制成的交联纤维,传统的酚醛纤维制备方法有熔融纺丝法和湿法纺丝法,后来出现了静电纺丝法。本文根据酚醛树脂的种类分别介绍了热固性、热塑性和热塑/热固混合酚醛树脂三类材料静电纺丝的研究进展。在改善酚醛纤维特性方面,综述了四种优化措施,包括加入无机盐、微波辐射辅助固化、非匀速阶梯式加热固化、氧化石墨烯修饰的静电纺丝法等。此外,对本实验室制备酚醛纤维的研究也进行了概述,阐述了酚醛纤维当前存在的问题及未来发展方向。 相似文献
90.
《Optimization》2012,61(2):99-112
In optimization, the literature on invariant definitions of convexity has largely centered on the notion of invexity. However, the connection with Morse theory and related geometric trends has not been recognized and results do not appear to be as impressive as those in topology. Our purpose is to improve the situation in optimization, and to clarify the relationship between these two trends. The main result is that the problem can be reduced to the case of functions of one variable. 相似文献