Reliability and uncertainty in the estimation of p<Emphasis Type="Italic">K</Emphasis><Subscript>a</Subscript> by least squares nonlinear regression analysis of multiwavelength spectrophotometric pH titration data

When drugs are poorly soluble then, instead of the potentiometric determination of dissociation constants, pH-spectrophotometric titration can be used along with nonlinear regression of the absorbance response surface data. Generally, regression models are extremely useful for extracting the essential features from a multiwavelength set of data. Regression diagnostics represent procedures for examining the regression triplet (data, model, method) in order to check (a) the data quality for a proposed model; (b) the model quality for a given set of data; and (c) that all of the assumptions used for least squares hold. In the interactive, PC-assisted diagnosis of data, models and estimation methods, the examination of data quality involves the detection of influential points, outliers and high leverages, that cause many problems when regression fitting the absorbance response hyperplane. All graphically oriented techniques are suitable for the rapid estimation of influential points. The reliability of the dissociation constants for the acid drug silybin may be proven with goodness-of-fit tests of the multiwavelength spectrophotometric pH-titration data. The uncertainty in the measurement of the pK _a of a weak acid obtained by the least squares nonlinear regression analysis of absorption spectra is calculated. The procedure takes into account the drift in pH measurement, the drift in spectral measurement, and all of the drifts in analytical operations, as well as the relative importance of each source of uncertainty. The most important source of uncertainty in the experimental set-up for the example is the uncertainty in the pH measurement. The influences of various sources of uncertainty on the accuracy and precision are discussed using the example of the mixed dissociation constants of silybin, obtained using the SQUAD(84) and SPECFIT/32 regression programs.     

Asymptotics of kernel error density estimators in nonlinear autoregressive models

The limiting distribution of the kernel error estimators in nonlinear autoregressive models is considered. It is shown that, at a fixed point, the distribution of the kernel error density estimator is normal without knowing the nonlinear autoregressive function. Supported by the NNSF of China(10671176&10771192).     

Goodness of fit: analysis of residuals

The goodness-of-fit problem is addressed and two among the more efficient tests presently available are revisited and discussed: the autocorrelation method and the sign test recently proposed by Paolo Minguzzi [J. Mol. Spectrosc. 209, (2001) 169], both based on residual analysis. A mathematical proof of the empirical relations needed in the sign test is proposed; it allows more insight in the comparison of both methods and shows that more information may be available from the sign test. Some differences of efficiency are pointed out in special cases, but finally these methods prove to be closely related. A general procedure is deduced that takes advantage of the practical usefulness of both approaches, of their efficiency and of the statistical information each of them can provide.     

Laminar and unstable burning velocities and Markstein lengths of hydrogen–air mixtures at engine-like conditions

Hydrogen offers an attractive alternative to conventional fuels for use in spark ignition engines. It can be burned over a very wide range of equivalence ratios and with considerable exhaust gas recirculation. These help to minimise pumping losses through throttleless operation and oxides of nitrogen (NO_x) production through reduced temperature. Full understanding of hydrogen-fuelled engine operation requires data on the laminar burning rate of hydrogen–air residuals under a wide range of conditions. However, such data are sparse. The present work addresses this need for experimental data. Spherically expanding H₂–air flames were measured at a range of temperatures, pressures, and equivalence ratios and with varying concentrations of residuals of combustion. Unstretched burning velocities, u_l, and Markstein lengths, L_b, were determined from stable flames. At the higher pressures, hydrodynamic and diffusional-thermal instabilities caused the flames to be cellular from inception and prohibited the derivation of values of u_l and L_b. The effect of pressure on the burning rate was demonstrated to have opposing trends when comparing stoichiometric and lean mixtures. The present measurements were compared with those available in the literature, and discrepancies were attributed to neglect, in some works, the effects of stretch and instabilities. From the present measurements, the effects of pressure, temperature, and residual gas concentration on burning velocity are quantified for use in a first step towards a general correlation.     

UPLC–MS as a powerful technique for screening the nonvolatile contaminants in recycled PET

The possibility of using recycled polyethylene terephthalate as a food contact material is being seriously considered, but the potential migration of nonvolatile compounds from it must be assessed to ensure that it is safe to do so. In the study presented here, four samples of recycled PET were each exposed to three food simulants under the harsh extraction conditions stipulated by European legislation regarding migration tests. The nonvolatile compounds that migrated from them were determined by ultra performance liquid chromatography–mass spectrometry using three different cone voltages, and both positive and negative ionization modes. A total of 36 chemical compounds were detected, some of which were identified, including common additives such as N,N′-di-beta-naphthyl-p-phenylenediamine (antioxidant) and 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)phenol (light stabilizer) as well as degradation compounds such as ethylene terephthalate dimers and trimers. In addition, specific migration values of three common components of polyethylene terephthalate (diethylene glycol, terephthalic acid, and isophthalic acid) were determined and found to occur at levels of <1 mg/kg—much lower than the specific migration limits stipulated by European legislation.     

A new model for estimating mass transfer coefficients for the extraction of ethanethiol with alkaline solutions in packed columns

The mathematical model for estimating the mass transfer coefficients for the ethanethiol extraction from gasoline, with alkaline solutions was established by processing the data obtained in a laboratory and in a pilot plant experiment. It allows the estimation of overall mass transfer coefficients, taking into account the dispersed phase velocity, the concentration of NaOH solution, the specific area and the porosity of the packing. The model’s parameters were statistical tested in order to confirm the accuracy of the model.     

横观各向同性轴对称问题的加权残数法及其工程应用

利用文[1,5]的理论,本文提出用两个调和函数的方法求解横观各向同性的轴对称问题,将它引入加权残数法,推得了一系列简洁的边界型最小二乘配法公式,就结构工程和岩土工程的两个例题作了计算,得到了有用的结论。本文的方法比列赫尼茨基的重调和函数法更为简便。     

滑动最小二乘插值函数在板弯曲问题上的应用

 利用滑动最小二乘插值函数作为加权残值法的试函数，分析了 该试函数的拟合特性，对试函数中的基函数以及权函数的选取提出了 建议；采用最小二乘配点法求出试函数中的系数，进而可得到定解问 题的近似解；利用该试函数对薄板的挠曲、中厚板的弯曲两个例子进 行了数值计算，并与理论结果或其它数值结果进行对比，结果表明， 该试函数适用于多种边值问题，且精度高. 该法简化了选择试函数的 过程，尤其适用于工程中的各种数值计算.