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191.
周慧  王中慧  晋卫军 《化学教育》2022,43(16):82-85
在处理电解质溶液的化学平衡理论中,有关离子的活度和活度系数的计算或估算都有比较严谨的理论公式或经验公式,而国内分析化学教材中关于经验公式的表述略显随意。以0.050 mol·L-1AlCl3水溶液中Cl-和Al3+的活度计算为例,结合国内外分析化学教材中关于活度系数计算的经验公式进行讨论。由计算结果可知,关于活度系数计算的经验公式需给出明确的使用条件。  相似文献   
192.
An approach for the analysis of large experimental datasets in electrochemical impedance spectroscopy (EIS) has been developed. The approach uses the idea of successive Bayesian estimation and splits the multidimensional EIS datasets into parts with reduced dimensionality. Afterwards, estimation of the parameters of the EIS-models is performed successively, from one part to another, using complex nonlinear least squares (CNLS) method. The results obtained on the previous step are used as a priori values (in the Bayesian form) for the analysis of the next part. To provide high stability of the sequential CNLS minimisation procedure, a new hybrid algorithm has been developed. This algorithm fits the datasets of reduced dimensionality to the selected EIS models, provides high stability of the fitting and allows semi-automatic data analysis on a reasonable timescale. The hybrid algorithm consists of two stages in which different zero-order optimisation strategies are used, reducing both the computational time and the probability to overlook the global optimum. The performance of the developed approach has been evaluated using (i) simulated large EIS dataset which represents a possible output of a scanning electrochemical impedance microscopy experiments, and (ii) experimental dataset, where EIS spectra were acquired as a function of the electrode potential and time. The developed data analysis strategy showed promise and can be further extended to other electroanalytical EIS applications which require multidimensional data analysis.  相似文献   
193.
In this paper, we address the accuracy of the results for the overdetermined full rank linear least‐squares problem. We recall theoretical results obtained in (SIAM J. Matrix Anal. Appl. 2007; 29 (2):413–433) on conditioning of the least‐squares solution and the components of the solution when the matrix perturbations are measured in Frobenius or spectral norms. Then we define computable estimates for these condition numbers and we interpret them in terms of statistical quantities when the regression matrix and the right‐hand side are perturbed. In particular, we show that in the classical linear statistical model, the ratio of the variance of one component of the solution by the variance of the right‐hand side is exactly the condition number of this solution component when only perturbations on the right‐hand side are considered. We explain how to compute the variance–covariance matrix and the least‐squares conditioning using the libraries LAPACK (LAPACK Users' Guide (3rd edn). SIAM: Philadelphia, 1999) and ScaLAPACK (ScaLAPACK Users' Guide. SIAM: Philadelphia, 1997) and we give the corresponding computational cost. Finally we present a small historical numerical example that was used by Laplace (Théorie Analytique des Probabilités. Mme Ve Courcier, 1820; 497–530) for computing the mass of Jupiter and a physical application if the area of space geodesy. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   
194.
With the three-dimensional symmetry and wide potential application, spherical array signal processing has been a hot research area for years. This paper devotes to the direction-of-arrival (DOA) estimation of the spherical arrays. Based on the orthogonality of the sensors’ location, MUSIC algorithm in spherical space is proposed, named as SH-MUSIC. Similar to beamspace MUSIC, spherical harmonics transformation is operated before MUSIC algorithm and a better performance is gotten because SH-MUSIC utilizes the array configuration’s orthogonality. On account of the transformation matrix’s orthogonality, spherical harmonics transformation is suggested to be operated firstly in other improved MUSIC algorithms without rejection, and it is demonstrated in beamspace MUSIC. In addition, owing to the tiny error between the steering vectors and the spherical harmonics with high order, sphere array data models including open sphere and rigid sphere are constructed. Simulation proves SH-MUSIC to be effective. Moreover, experimental data from a rigid sphere microphone array is dealt with by SH-MUSIC and the DOAs are estimated accurately.  相似文献   
195.
The relationship of the phase morphology of polypropylene/polyethylene‐terephthalate (PP/PET) blends and their corresponding compatibilized blends with composition was investigated using digital image analysis. A diameter, d g , was defined and calculated to discuss the phase morphology of this polymer blend system. A figure‐estimation method was introduced to determine the width of the distribution of d g . Based on the method, it is proven that the distribution of d g obeys a log‐normal distribution and consequently, the distribution width, σ was calculated. Further, a fractal dimension, D f , was introduced to describe the distribution of main sizes of the particles of the dispersed phase. The results showed that, while d g increased with the concentration of the dispersed phase, σ and D f show different dependence relations on composition;σ increases monotonously but D f shows a maximum at a PET content of 30%, indicating that, even though the whole size distribution is much broader, the distribution of the main body of size becomes more uniform when the content of PET is less than 30%.  相似文献   
196.
Modern radiometric analytics demands a complex consideration of nuclear and electron shell processes, if more pretentious aims are envisaged. As an example the small variation of decay rates of radionuclides presents possibilities for information on chemical situations of decaying atoms. In principle this phenomenon is well known since many years, but now the situation is such that, e.g. in 99mTc internal conversion, a full agreement of the difficult experiments and the respective theory was established. The secondary emission of X-rays as a consequence of high excitation of electron shells in combination with nuclear transitions supplies another example for a methodical progress of radiometry. Investigations on 51Cr as an electron capture nuclide have shown that chemically induced variations of the Kα to Kβ X-ray intensity ratio is at least qualitatively understood.  相似文献   
197.
This paper provides simulation comparisons among the performance of 11 possible prediction intervals for the geometric.mean of a Pareto distribution with parameters (αB, ). Six different procedures were used to obtain these intervals , namely; true inter -val , pivotal interval , maximum likelihood estimation interval, centrallimit teorem interval, variance stabilizing interval and a mixture of the above intervals . Some of these intervals are valid if the observed sample size m,are large , others are valid if both, n and the future sample size m, are large. Some of these intervals require a knowledge of α or B, while others do not. The simulation validation and efficiency study shows that intervals depending on the MLE's are the best. The second best intervalsare those obtained through pivotal methods or variance stabilization transformation. The third group of intervals is that which depends on the central limit theorem when λ is known. There are two intervals which proved to be unacceptable under any criterion.  相似文献   
198.
199.
Different discretizations of the gradient and curl operators are considered for a staggered grid in a height‐based terrain‐following coordinate system. A combination of discrete operators is identified that guarantees the mimetic property that the curl of the gradient of any scalar vanishes identically. The result is illustrated with some numerical examples. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   
200.
Studies of fluid-structure interactions associated with flexible structures such as flapping wings require the capture and quantification of large motions of bodies that may be opaque. As a case study, motion capture of a free flying Manduca sexta, also known as hawkmoth, is con-sidered by using three synchronized high-speed cameras. A solid finite element (FE) representation is used as a reference body and successive snapshots in time of the displacement fields are reconstructed via an optimization procedure. One of the original aspects of this work is the formulation of an objective function and the use of shadow matching and strain-energy regularization. With this objective function, the authors penalize the projection differences between silhou-ettes of the captured images and the FE representation of the deformed body. The process and procedures undertaken to go from high-speed videography to motion estimation are dis-cussed, and snapshots of representative results are presented. Finally, the captured free-flight motion is also characterized and quantified.  相似文献   
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