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1.
During the course of our investigation of the electron transfer properties of some redox species through highly hydrophobic
long chain alkanethiol molecules on gold in aqueous and non-aqueous solvents, we obtained some intriguing results such as
unusually low interfacial capacitance, very high values of impedance and film resistance, all of which pointed to the possible
existence of a nanometer size interfacial gap between the hydrophobic monolayer and aqueous electrolyte. We explain this phenomenon
by a model for the alkanethiol monolayer—aqueous electrolyte interface, in which the extremely hydrophobic alkanethiol film
repels water molecules adjacent to it and in the process creates a shield between the monolayer film and water. This effectively
increases the overall thickness of the dielectric layer that is manifested as an abnormally low value of interfacial capacitance.
This behaviour is very much akin to the ‘drying transition’ proposed by Lum, Chandler and Weeks in their theory of length
scale dependent hydrophobicity. For small hydrophobic units consisting of apolar solutes, the water molecules can reorganize
around them without sacrificing their hydrogen bonds. Since for an extended hydrophobic unit, the existence of hydrogen bonded
water structure close to it is geometrically unfavourable, there is a net depletion of water molecules in the vicinity leading
to the possible creation of a hydrophobic interfacial gap. 相似文献
2.
Kurt M. Anstreicher 《Mathematical Programming》1997,76(1):245-263
We consider the construction of small step path following algorithms using volumetric, and mixed volumetric-logarithmic, barriers.
We establish quadratic convergence of a volumetric centering measure using pure Newton steps, enabling us to use relatively
standard proof techniques for several subsequently needed results. Using a mixed volumetric-logarithmic barrier we obtain
an O(n
1/4
m
1/4
L) iteration algorithm for linear programs withn variables andm inequality constraints, providing an alternative derivation for results first obtained by Vaidya and Atkinson. In addition,
we show that the same iteration complexity can be attained while holding the work per iteration to O(n
2
m), as opposed to O(nm
2), operations, by avoiding use of the true Hessian of the volumetric barrier. Our analysis also provides a simplified proof
of self-concordancy of the volumetric and mixed volumetric-logarithmic barriers, originally due to Nesterov and Nemirovskii.
This paper was first presented at the 1994 Faculty Research Seminar “Optimization in Theory and Practice”, at the University
of Iowa Center for Advanced Studies. 相似文献
3.
4.
关于非平行板电容器电容计算的讨论 总被引:4,自引:3,他引:1
用串联方法计算非平行板电容器的电容,简便地得到与其他方法相同的结果。 相似文献
5.
In this paper, the chronoamperometry was used to study the charging processes of polyethylenedioxythiophene (PEDOT) modified electrodes in the potential range where PEDOT was in the oxidized state. The results show that the charging behaviors of the PEDOT films are well agreed with the exhausted finite diffusion model. The dependence of the capacitance values of the films on potential and concentration of solution was also studied in this potential range. 相似文献
6.
Using well-cycled, thin composite graphite electrodes we analyze carefully the limitations of potentiostatic and galvanostatic intermittent titration techniques (PITT and GITT, respectively) for determination of the differential (incremental) intercalation capacitance, Cdif, and the chemical diffusion coefficient, D, of Li ions in these ion-insertion electrodes (IIEs). We demonstrate the superiority of the GITT over PITT to determine these quantities as the former technique allows for a more accurate determination of Cdif and hence D which closely approach to the spinodal domain related to the first-order phase transition during ion-insertion. We show that GITT is also more effective in eliminating the parasitic contributions of background currents to the total measured response. A pronounced difference in the initial, intrinsic kinetics of formation of a new phase in the bulk of the old one has been observed depending on the direction of titration (phases less saturated with Li are formed faster during deintercalation than the Li-rich phases in the course of intercalation). 相似文献
7.
As an adjunct to the regression analysis of differential capacitance curves, which allows refining the adsorption parameters, a program, which takes into account possible errors in volume concentrations of organic substances, is developed. Using this procedure, the earlier data on the differential capacitance of a mercury electrode in aqueous solutions of normal butanol (1-BuOH) containing either 0.1 M NaF or 0.05 and 0.5 M Na2SO4 as the supporting electrolyte are analyzed. This allows obtaining the most accurate values of adsorption parameters for the systems mentioned above within the framework of the model of two parallel capacitors and the Frumkin isotherm. It is shown that, when a linear dependence of the intermolecular interaction parameter on the electrode potential is taken into account, the standard deviation of experimental capacitance values from those calculated using the mentioned model is 6.8–8.8%, which points to very high accuracy of this phenomenological model. 相似文献
8.
In the system of SDS/n-C5H11OH/n-C7H16/H2O with the weight ratio of SDS/n-C5H11OH/H2O system at5.0/47.5/47.5, the upper phase of the system was W/O microemulsion, and the lower phase was the bicontinuous microemulsion. When the n-heptane content was less than 1%, with the increase of the n-heptane content, the capacitance (Co, Cod) in the upper phase (W/O) dropped, the capacitance (CB1, CBld) in the lower phase (BI) raised. At the same time, the W/O-BI inteffacial potential (ΔE), capacitance (Ci), and charge-transfer current (ict) decreased.After the n-heptane content reached 1%, with the increase of the n-heptane content, ΔE, Ci and ict demonstrated no significant change. 相似文献
9.
3-Mercaptopropionic acid monolayer protected gold nanoclusters (MPA-MPCs) were synthesized and characterized by transmission electorn microscopy,UV-Vis spectroscopy,X-ray photoelectron spectroscopy and Fourler transform infrared spectroscopy.The exact value of quantized double-layer capacitance of MPCs in aqueous media was obtained by differential pulse voltammograms. 相似文献
10.
S. K. Tobia Y. A. Gawargious M. F. El-Shahat 《Fresenius' Journal of Analytical Chemistry》1973,265(1):23-24
Summary Simple and accurate methods are described for the microdetermination of arsenate and arsenite ions using 12- and 14-fold amplification reactions. The arsenate method is based upon reaction with calcium iodate and iodometric titration of the liberated iodate, whereas the arsenite method depends upon reaction with iodine and oxidation of the resulting iodide with bromine. This is followed by iodometric titration of the iodate in addition to the arsenate present in solution. The overall recovery amounts to 99.51 and 99.63% for arsenate and arsenite respectively.
Mikrobestimmung von Arsenat- und Arsenitionen mit Hilfe einer Vervielfachungsreaktion mit Jodat bzw. Jod
Zusammenfassung Ein einfaches und genaues Verfahren mit 12- bzw. 14facher Vervielfachung wird beschrieben. Die Arsenatbestimmung beruht auf der Reaktion mit Calciumjodat und jodometrischer Titration des freigesetzten Jodats, die Arsenitbestimmung auf der Reaktion mit Jod, Oxydation des erhaltenen Jodids mit Brom und jodometrischer Titration des gebildeten Jodats zusammen mit dem aus dem Arsenit entstandenen Arsenat. 99,51 bzw. 99,63% von eingesetztem Arsenat bzw. Arsenit konnten wiedergefunden werden.相似文献