Superheating Limit of Boiling n-Hexane Spinodal Decomposition Versus Nucleation Process

Two predicative theories for superheating limits of a boiling liquid are considered in this work. In the nucleation picture, classical homogeneous nucleation theory is used to calculate superheating temperature at various pressures. In spinodal decomposition picture, stability limits are taken as the superheating temperature. A perturbed-hard chain equation of state was developed and used for the purpose of calculating mechanical stability limit. Calculations are done for the case of normal hexane at different pressures and compared with experimental results. Classical nucleation theory gives good prediction at negative and smaller pressures. While near critical pressure, spinodal picture seems to be more accurate.     

An atlas of forecasted molecular data. 2. Vibration frequencies of main-group and transition-metal neutral gas-phase diatomic molecules in the ground state

This atlas of diatomic-molecular vibration frequencies parallels the previously offered Atlas of Internuclear Separations. The Atlas was produced by mining the data from Huber and Herzberg and training neural network software to forecast new data. New protocols were employed with the powerful software, which was originally designed for forecasting the financial markets. The Atlas presents 1920 additional vibration frequencies for use until critical tables are available to fill the needs more precisely. The precision of the predictions is characterized by the average fractional 1% confidence limit, that is, 10.66%. The accuracies of the predictions are determined in two ways. First, 221 of the 224 Huber and Herzberg data values used for training and validation fall within the prediction confidence limits or fall outside by less than 10% of the Huber and Herzberg values, and 181 values agree (within the limits). Second, 87 of 101 comparison data values, consisting of literature data and some additional Huber and Herzberg values, fall within the prediction confidence limits or fall outside by less than half the prediction values, and 44 of the 101 values agree (within the limits).     

Limits of detection and decision. Part 1

Extensive Monte Carlo studies of instrumental limits of detection were performed on a simple univariate chemical measurement system having homoscedastic, Gaussian measurement noise and using ordinary least squares (OLS) processing of tens of millions of independent calibration curve data sets. It was found that prediction interval-based experimental detection limits were significantly negatively biased, in both the net response domain and the chemical content domain, resulting in substantially higher rates of false negatives than specified via customary critical t values. The diagnostic fix for the bias problem provided clear proof that hypothesis-based detection limits need not be unique, even as distributions of random variates, if the alternate hypothesis is non-unique. It was also demonstrated that hypothesis-based decision and detection limits have finite support that does not include the region near zero analyte content, so that both have finite moments and finite confidence intervals.     

Limits of detection, identification and determination: a statistical approach for practitioners

 For the estimation of the limits of detection, identification and determination, considerations from analytical practice were applied to the statistics of the calibration line and its prediction interval. The detection limit was the concentration calculated from the maximum height of the prediction interval at zero spiking concentration. The identification limit was twice the detection limit and was the lowest concentration that could safely be detected. The determination limit was the lowest concentration fulfilling three criteria: 1. None of the signals resulting from determination limit concentration should interfere with any signal from detection limit concentration, thus providing an unambiguous separation between the two limits. 2. Recovery should be between 70% and 120%. 3. Lowest and highest predictable signal at determination limit concentration should not deviate more than ± 30% from the average. Practical analytical guidance and the necessary mathematical formulae are presented. Received: 12 November 1997 · Accepted: 7 December 1997     

高溶解性盐水体系热力学模型预测能力的比较研究I: 二元体系

用原始Pitzer模型、扩展的Pitzer模型、Pitzer-Simonson-Clegg模型、S-MSA模型和BET模型分别对LiCl-H2O, LiBr-H2O, CaCl2-H2O, Mg(NO3)2-H2O, MnCl2-H2O和Mn(NO3)2-H2O等六种不同体系的热力学性质进行描述, 考察了各种模型的预测能力. 结果表明原始Pitzer模型不能准确描述高浓电解质溶液的性质; 扩展的Pitzer模型虽然能较准确地描述某些体系高浓度的热力学性质, 但预测能力不足; Pitzer-Simonson-Clegg模型对高浓盐水体系热力学性质具有一定的预测能力, 但拟合参数所用的最大浓度与溶解度相差很大时, 外推饱和点的热力学性质则会出现较大偏差; S-MSA模型虽然可以将拟合参数的浓度范围扩大到饱和, 但没有外推能力, 而且需要溶液的密度数据, 这限制了该模型的广泛应用; BET模型对这六种体系均体现出很强的预测能力, 预测结果准确, 且模型参数少, 物理意义明确, 该模型可用于熔盐水化物相变储能材料的设计.     

Comparison of doping limits among sonochemically prepared metal-doped TiO2 nanopowders in view of physicochemical properties

According to binding energy calculations in a unit cell model of anatase TiO₂, the doping limits for Cr, V, W, Mo, Zr, and Nb are predicted to increase in this order. In our experimental test of doping limits, Cr and W are considered in this series of transition metals, since their low doping limits suggest greater difficulty of doping into anatase structure than the others, thereby providing a challenging test for the prediction. Besides, noble metals such as Ag and Pt are selected for doping into TiO₂ for comparison. Thus, our investigation includes twofold research activities. One is to prepare metal-doped TiO₂ nanopowders of four different kinds, and the other is to determine the doping limit of each resulting powder. For the former, a sonochemical process has been used to produce metal-doped TiO₂ nanoparticles. For the latter, we resorted to electron probe microanalysis. In addition, we performed analysis by X-ray diffraction, transmission electron microscopy, and diffuse reflectance spectroscopy, as well as photocatalytic reaction with methylene blue. Thus, the resulting physicochemical properties of our metal-doped nanoparticles are expected to provide a basis for comparison of doping limits among them.     

Simultaneous determination of salicylic acid and salicylamide in biological fluids

A new methodology for the simultaneous determination of salicylic acid and salicylamide in biological fluids is proposed. The strong overlapping of the fluorescence spectra of both analytes makes impossible the conventional fluorimetric determination. For that reason, the use of fluorescence decay curves to resolve mixtures of analytes is proposed; this is a novel technique that provides the benefits in selectivity and sensitivity of the fluorescence decay curves. In order to assess the goodness of the proposed method, a prediction set of synthetic samples were analyzed obtaining recuperation percentages between 98.2 and 104.6%. Finally, a study of the detection limits was done using a new criterion resulting in values for the detection limits of 8.2 and 11.6 μg L(-1) for salicylic acid and salicylamide respectively. The validity of the method was tested in human serum and human urine spiked with aliquots of the analytes. Recoveries obtained were 96.2 and 94.5% for salicylic acid and salicylamide respectively.     

Establishment of multivariate specifications for food commodities with discriminant partial least squares

A novel method for establishing multivariate specifications of food commodities is proposed. The specifications are established for discriminant partial least squares (DPLS) by setting limits on the predictions of the DPLS model together with Hotelling T² and square error of prediction (SPE). These limits can be tuned depending on whether type I error (i.e. a correct sample is declared out-of-specification) or type II error (i.e. an out-of-specification sample is declared within specifications) need to be minimized. The methodology is illustrated with a set of NIR spectra of Italian olive oils, corresponding to five regions and the class Liguria is the class of interest. The results demonstrate the possibility of establishing multivariate specification for olive oils from the Liguria region on the basis of spectral data obtaining type I and type II errors lower than 5%.     

Estimation of rate constants from growth and decay data

Many experiments in chemical kinetics are initiated by a fast pulse, such as electric discharge, shock wave, flash lamp, or laser. After this pulse one observes the production and subsequent decay of a reactive intermediate. One then postulates a mechanism and adjusts the associated rate constants so as to minimize the difference between the results of the experiment and the prediction of the mechanism. The parameters to be estimated are usually strongly correlated, so that it is not possible to determine them separately. These estimated parameters are of little value unless we can also estimate statistically valid confidence limits for them. The difficulties are discussed which frequently arise in estimating parameters and confidence limits for a kinetic mechanism which is widely used in interpreting laser excitation and fluorescence measurements, that is, first-order production and decay. These difficulties, and methods for dealing with them, are illustrated with realistic data. The estimation problem is particularly ill conditioned when the production and loss rates are nearly equal. In some experimental systems this can be avoided, but in others it is inevitable.     

INAA with gamma-gamma coincidence for selenium determination in food

Selenium detection limits of INAA are normally above its concentration in most biological materials. Gamma-gamma coincidence methodology can be used to improve the detection limits and uncertainties in the determination of selenium. Here, some edible parts of plants were measured using a HPGe detector equipped with a NaI(Tl) active shielding, producing spectra both in normal and coincidence modes. The results presented the reduction of the detection limits of selenium by a factor of 2 to 3 times and improvement in the uncertainty of up to 2 times.     

QSPR Modeling of Potentiometric Mg2+/Ca2+ Selectivity for PVC‐plasticized Sensor Membranes

The development of novel ionophores for ion‐selective sensors is a time‐consuming and tedious process requiring synthesis of candidate substances, preparation of plasticized polymeric membranes, and their thorough characterization with traditional protocols to assess sensitivity, selectivity and detection limits for target ions. The vast amount of literature data accumulated on various ion‐selective sensors allows for significant facilitation of the development through in silico experiments. In this report, we performed the feasibility study on the prediction of potentiometric Mg²⁺/Ca²⁺ selectivity for various amide ligands using quantitative structure‐property relationship (QSPR) modeling. The approach proved to be promising for ionophore screening purposes with achieved precision in prediction of the selectivity coefficient logK(Mg²⁺/Ca²⁺) of 0.5 in the range from ?1.7 to +2.3. The study also shows a route for prediction of new potential ionophores with high selectivity values.     

14 MeV neutron activation analysis applied to a non-aqueous flowing system

The feasibility and advantages of fast neutron activation analysis in a non-aqueous flowing system, using economical irradiation techniques are outlined. The application of the method to the determination in solution of elements producing isotopes with half lives in the range 588—29.4 sec, the selection of the optimum flow rate to minimise interferences for each element, and their limits of detection are also given. A method for the prediction of the optimum flow rate, on a given system, for the determination of any element producing an isotope of known half life is also given.     

Determination of low analyte concentrations by near-infrared spectroscopy: effect of spectral pretreatments and estimation of multivariate detection limits

Near infrared spectroscopy (NIRS) was used in combination with partial least squares (PLS) calibration to determine low concentrated analytes. The effect of the orthogonal signal correction (OSC) and net analyte signal (NAS) pretreatments on the models obtained at concentrations of analyte near its detection limit was studied. Both pretreatments were found to accurately resolve the analyte signal and allow the construction of PLS models from a reduced number of factors; however, they provided no substantial advantage in terms of %RSE for the prediction samples. Multiple methodologies for the estimation of detection limits could be found in the bibliography. Nevertheless, detection limits were determined by a multivariate method based on the sample-specific standard error for PLS regression, and compared with the univariate method endorsed by ISO 11483. The two methods gave similar results, both being effective for the intended purpose of estimating detection limits for PLS models. Although OSC and NAS allow isolating the analyte signal from the matrix signal, they provide no substantial improvement in terms of detection limits. The proposed method was used to the determine 2-ethylhexanol at concentrations from 20 to 1600 ppm in an industrial ester. The detection limit obtained, round 100 ppm, testifies to the ability of NIR spectroscopy to detect low concentrated analytes.     

Exploring background variability of a low-level (quartz) gas proportional counter using pulse shape and distribution analysis

The NIST low-level beta counting system is designed to capture digitally and timestamp each event for retrospective analysis. As a result, low and stable backgrounds are achieved and lead to extremely low detection and quantification limits for measuring, e.g., ¹⁴C of atmospheric gases and aerosol. The objective here is to explore the variability of the background count rate (counts per day) of several small (1 mL) freshly-assembled gas proportional counters (GPCs). The mean is 14.0 day^?1 with 95 % confidence limits 11.2–16.8 day^?1. The raw count per day data was non-normal and so a Log transformation was applied to achieve normality and to rigorously compute normal tolerance limits. Back in the original space such (95 % confidence, 95 % coverage) tolerance limits were 2.5–47.8 day^?1. These limits are taken as acceptance criteria for any GPCs assembled in the future.     

Studies on Lattice Parameter,Molar Volume and Excess Molar Volume of Pb-based a-phase Solid Solution in Pb-Sn-Cd Ternary System

The lattice parameters a and the molar volumes Km of Pb-based a-phase solid solutions in the Pb-Sn-Cd ternary system were determined by means of X-ray diffraction. The lattice parameters a vary linearly with the molar fractions, the molar volumes show a positive deviation from the ideal solution behaviour, and the contribution of the solute Cd to the excess molar volumes V is much larger than that of the solute Sn. According to Vegard' s law orsub-regular solution model, the relationship between the experimental data of a or Vm andthe compositions of alloy is obtained by the mathematic regressive method, the prediction precisions of the both formulae are within the limits of experiment error.     

端视ICP-AES系统分析性能研究──Ⅰ．在稀土分析中的应用

本工作通过比较端视与侧视ICP的分析性能，研究了端视ICP系统对稀土元素的分析特性。高频发生器输出功率与载气流量对端视与侧视ICP激发特性的影响没有明显差异，取光方式的不同是二者分析性能差异的根本原因。端视ICP由于取光时避开了产生连续背景的环形热区和截取了整个中心通道的光谱．其背景减小，谱线强度增强，获得较好的测定下限。对14种稀土元素测定下限的比较表明：端视ICP比铡视ICP下降10-30倍。     

Electrical surface resistivity of conductive polymers - A non-Gaussian approach for determination of confidence intervals

Polyanilines doped with different acids (HCl, H₂SO₄ and dodecylbenzenesulfonic acid, DBSA) were prepared and their surface electrical conductivities were characterized in a four-probe device, connected to a real-time data acquisition board. Collected data were synchronized and conductivity calculations were performed. The conductive behavior of the polyanilines was investigated along the electrification time. This allowed for introduction of a non-Gaussian technique for determination of the confidence intervals of surface resistivity data. It is shown that the distribution of experimental surface resistivity data does not follow a normal probability distribution function (PDF). Thus, ordinary assumptions related to normal distribution of the experimental errors are wrong and must be corrected for proper determination of the confidence limits of measured resistivity values. It is shown here that confidence limits of resistivity values are asymmetrical and that distribution of experimental values can follow multimodal distributions.     

端视ICP－AES系统分析性能研究──Ⅰ．在稀土分析中的应用

本工作通过比较端视与侧视ＩＣＰ的分析性能，研究了端视ＩＣＰ系统对稀土元素的分析特性。高频发生器输出功率与载气流量对端视与侧视ＩＣＰ激发特性的影响没有明显差异，取光方式的不同是二者分析性能差异的根本原因。端视ＩＣＰ由于取光时避开了产生连续背景的环形热区和截取了整个中心通道的光谱，其背景减小，谱线强度增强，获得较好的测定下限。对１４种稀土元素测定下限的比较表明：端视ＩＣＰ比铡视ＩＣＰ下降１０－３０倍。