The main objective of this paper is to introduce principal component analysis and two robust fuzzy principal component algorithms
as useful tools in characterizing and comparing rime samples collected in different locations in Poland (2004–2007). The efficiency
of the applied procedures was illustrated on a data set containing 108 rime samples and concentration of anions, cations,
HCHO, as well as pH and conductivity. The fuzzy principal component algorithms achieved better results mainly because they
are more compressible than classical PCA and very robust to outliers. For example, a three component model, fuzzy principal component analysis-first component (FPCA-1) accounts for 62.37% of the total variance and fuzzy principal component analysis-orthogonal (FPCA-o) 90.11%; PCA accounts only for 58.30%. The first two principal components explain 51.41% of the total variance in
the case of FPCA-1 and 79.59% in the case of FPCA-o as compared to only 47.55% for PCA. As a direct consequence, PCA showed
only a partial differentiation of rime samples onto the plane or in the space described by different combination of two or
three principal components, whereas a much sharper differentiation of the samples, regarding their origin and location, is
observed when FPCAs are applied.
相似文献
Performed tests showed that at 298?K hard coals sorb relatively small amounts of hydrogen. Those amounts depend on carbon and oxygen content in tested coals. The most considerable amounts of hydrogen are sorbed by coals characterized by strong surface hydrophobicity and high content of aliphatic hydrocarbons. The hydrophilic nature of coal surface does not lead to higher sorption of hydrogen. It was found that the change in amount of sorbed hydrogen is closely related to the moisture. For high moisture coal a significant decrease in hydrogen sorption is observed. Also tests on hydrogen desorption on hard coals were carried out using method of lowering hydrogen pressure above the sorbent. Obtained results showed that tested coals desorb various amounts of hydrogen. Process of sorption is reversible only for some coals, while for the others the desorption isotherm partially lies beneath the sorption isotherm, which indicates that in addition to hydrogen some other chemical substances are emitted from coal. 相似文献
JPC – Journal of Planar Chromatography – Modern TLC - In a previous paper we discussed the possibility of fractionating the essential oils of different sage species by low-temperature... 相似文献
A selective and sensitive method is proposed for the determination of mercury by anodic stripping voltammetry after its preconcentration
from the gas phase. Mercury from the sample solution is reduced to elemental Hg by SnCl2 and volatilized by the bubbles of a carrier gas. The gas containing mercury vapour is dried and passed through a capillary
onto a gold coated graphite electrode. An anodic stripping voltammogram is recorded from 0.1 mol/l HClO4+3×10-3 mol/l HCl solution. The calibration curve is linear from 1×10-9 to 4×10-8 mol/l Hg(NO3)2. The absolute detection limit is 0.46 ng Hg. The relative standard deviations for 4×10-9 mol/l and 2×10-8 mol/l Hg(NO3)2 are 9.8% and 6.1%, respectively (n=5).
Received: 18 December 1995/Revised: 16 April 1996/Accepted: 20 April 1996 相似文献
The voltammetric procedure for determination of traces of Cr(VI) [Anal. Chim. Acta (1992) 262:103] was modified by changing the temperature of the measurements. It was found that at the temperature of 40 °C the time of decrease of the Cr(III) signal was shortened from 30 to 5 min. As a result the total analysis time was drastically shortened. The modified procedure does not show any disadvantage as compared to the original method. The results of Cr(VI) determination by the modified procedure are less affected by Cr(III) as compared to the original method. The detection limit of the method was 2.5 × 10-11 mol L-1 (1.2 ng L-1). The validation of the modified procedure was performed by comparison of the results of analyses of tap and river water samples with those obtained using original procedure. 相似文献
Soluble products obtained from the oxidation of four types of coal, each characterised by different degree of coalification
and different degree of sulphur content, are studied. The coals are oxidised with peracetic acid (PAA) and nitric acid. Analyses
are performed by Atmospheric Pressure-Temperature Programmed Reduction (AP-TPR) and Fourier Transform Infrared Spectroscopy
(FTIR). The soluble products contain much more sulphur than the insoluble products of oxidation. The products obtained from
the reaction with HNO3 contain higher amounts of inorganic sulphur compounds, while those obtained from the reaction with PAA are characterised
by an increased content of organic sulphur species. 相似文献
The two adsorptive stripping voltammetric approaches for detection and quantitative determination of diethyl (2E)-2-{(2E)-[1-(4-methylphenyl)imidazolidin-2-ylidene]hydrazinylidene}butanedioate (DIB)—a novel molecule of medical importance—using two sensitive sensors based on modified glassy carbon electrodes as reusable sensors, were developed for the first time. The proposed electrochemical methods are based on adsorptive/reductive behaviour of DIB at two modified carbonic electrodes: a bismuth film-modified glassy carbon electrode (BiF/GCE) and a lead film-modified glassy carbon electrode (PbF/GCE). The electron gain mechanism for the electrochemical reduction of DIB on both developed sensors was proposed for the first time. To achieve the highest sensitivity in adsorptive stripping determinations, various experimental variables (e.g. the composition and pH of the supporting electrolytes, deposition conditions of bismuth and lead films, concentrations of plating solutions, accumulation times and potentials of DIB, etc.) were extensively examined. The comparison of validation parameters obtained during the determination of DIB at two sensors was presented. The excellent linear correlation was found between the monitored adsorptive stripping voltammetric peak current and the DIB concentration in the range of 15–600 μg L−1 at an accumulation time of 30 s (with LOD = 4.2 μg L−1 and LOQ = 14.0 μg L−1) using the BiF/GCE as a sensor. Furthermore, the excellent linear relationship was confirmed between the monitored adsorptive stripping voltammetric peak current and the DIB concentration in the range of 9–900 μg L−1 at an accumulation time of 10 s (with better LOD = 1.5 μg L−1 and LOQ = 5.0 μg L−1), employing the PbF/GCE as a sensor. The two optimized adsorptive stripping voltammetric approaches—as facile, sensitive, reliable and inexpensive—were successfully used as first methods for the quantitative analysis of a novel anticancer agent (DIB) in its pure pharmaceutically acceptable form. However, the practical applicability of square-wave adsorptive stripping voltammetric determination of the electroactive DIB molecule at a PbF/GCE, as the modified electrode of higher sensitivity, was presented after its successful solid phase extraction from a real serum sample.
Observation that rates of dehydrobromination of trans-β-bromostyrene (1) and the Hofmann degradation of tetrabutyl ammonium cation depend on strength of base in different ways and that treatment of 1 with base results in fast abstraction of the β-proton imply the possibility that the dehydrobromination of 1 could proceed via α-elimination and Ph migration. In order to clarify this question, β-13C-labeled 1 was obtained and subjected to PTC dehydrobromination which proceeds without migration of Ph. The obtained results are consistent with an irreversible E1cB mechanism. 相似文献
A model of monolayer adsorption of binary liquid mixtures on homogeneous and heterogeneous solid surfaces involving association of one component in the bulk phase is discussed. Suitable model calculations, illustrating association and heterogeneity effects, have been performed according to an equation derived for adsorption excess. This equation has been examined by using the experimental data of adsorption of alcohols from benzene andn-heptane on silica gel.
Adsorptionsmodell für die Grenzfläche Feststoff-Flüssigkeit unter Berücksichtigung der Assoziation in der Flüssigkeitsphase
Zusammenfassung Es wird ein Adsorptionsmodell binärer, flüssiger Mischungen an homogenen und heterogenen Oberflächen von Feststoffen unter Beachtung der Assoziation eines der Bestandteile in der Flüssigkeitsphase diskutiert. Mit der aus dem Oberflächenüberschuß abgeleiteten Gleichung wurden entsprechende Modellberechnungen durchgeführt, die die mit Assoziation und Heterogenität verbundenen Effekte illustrieren. Die Gleichung wurde für die experimentellen Daten der Alkoholadsorption aus Benzol undn-Heptan an Kieselgel überprüft.
An equation for multilayer adsorption from multicomponent liquid mixtures on solid surfaces1 has been examined. For this purpose experimental adsorption data for four alcohols from benzene/n-heptane mixture on silica gel have been measured. Average number of the adsorbed layers, heterogeneity parameter and capacity of the surface phase have been evaluated by using the equation mentioned above.
Mehrschichten-Adsorption von Alkoholen aus Benzol/n-Heptan-Mischung an Silica Gel
Zusammenfassung Eine Gleichung für Mehrschichten-Adsorption an festen Oberflächen1 aus Mehrkomponentenlösungen wurde getestet. Zu diesem Zweck wurden experimentelle Daten für die Adsorption von vier Alkoholen aus Benzol/n-Heptan-Mischung an Silica Gel herangezogen. Der Mittelwert für die Anzahl der Adsorptionsschichten, der Heterogenitätsparameter und die Kapazität der Oberflächenphase wurde aus dieser Gleichung berechnet.