The apparent molar volumes, V,2, of glycine, L-alanine, DL--amino-n-butyric acid, L-valine, and L-leucine have been determined in aqueous 0.25, 0.75, 1.0, and 1.5 mol-dm–3 tetraethylammonium bromide (TEAB) solutions by density measurements at 298.15 K. These data have been used to calculate the infinite dilution apparent molar volumes, V2,m, for the amino acids in aqueous tetraethylammonium bromide and the standard partial molar volumes of transfer (trV2,m) of the amino acids from water to the aqueous salt solutions. The linear correlation of V2,m for a homologous series of amino acids has been utilized to calculate the contribution of the charged end groups (NH3+, COO–), CH2 group, and other alkyl chains of the amino acids to V2,m. The results of the standard partial molar volumes of transfer from water to aqueous tetraethylammonium bromide have been interpreted in terms of ion–ion, ion–polar, and hydrophobic–hydrophobic group interactions. The volume of transfer data suggest that ion–ion or ion–hydrophilic interactions are predominant in the case of glycine and alanine, and hydrophobic–hydrophobic group interactions are predominant in the case of DL--amino butyric acid, L-valine, and L-leucine. 相似文献
The excess partial molar enthalpies, the vapor pressures, and the densities of dimethylsulfoxide (DMSO)–H2O mixtures were measured and the excess partial molar Gibbs energies and the partial molar volumes were calculated for DMSO and for H2O. The values of the excess partial molar Gibbs energies for both DMSO and H2O are negative over the entire composition range. The results for the water-rich region indicated that the presence of DMSO enhances the hydrogen bond network of H2O. Unlike monohydric alcohols, however, the solute-solute interaction is repulsive in terms of the Gibbs energy. This was a result of the fact that the repulsion among solutes in terms of enthalpy surpassed the attraction in terms of entropy. The data in the DMSO-rich region suggest that DMSO molecules form clusters which protect H2O molecules from exposure to the nonpolar alkyl groups of DMSO. 相似文献
Partial molar volumes at infinite dilution, V02, of alkali–metal halides (LiCl, NaCl KCl RbCl CsCl, NaBr, KBr, KI), tetra-n-alkylammonium bromides, R4NBr (R=Me, Et, n-Pr, n-Bu, n-Pen), NaBPh4, and Ph4PCl have been determined in binary solvent mixtures of water with 2-methyl-2-butanol covering the water-rich region and the alcohol-rich region at 298.15 K. V02 for alkali–metal halides show relatively little dependence on the solvent composition. However, in the case of hydrophobic electrolytes the observed effects are more pronounced. A good linear dependence between V02(R4NBr) and the molecular weight of the tetra-n-alkylammonium cation is found. Limiting single-ion volumes have been obtained using the assumption that V0(Ph4P+)–V0(BPh–4)=2.0 cm3-mol–1. The trends in the single-ion volumes are discussed in both solvent regions. 相似文献
The densities of supercritical CO2-tetrahydrofuran (cosolvent) binary mixture weremeasured at temperatures in range of 308.15 to 323.15 K and at pressure up to 16.5 MPa.The concentrations of tetrahydrofuran were from 0 to 0.57 mol/L.The partial molar volume of tetrahydrofuran was calculated based on the relationship between the density of the mixture and the concentration of the cosolvent.It is observed that the partial molar volume of the cosolvent is negative and the absolute value decreases with increasing pressure and the concentration of the cosolvent. 相似文献
Changeable size moving window partial least squares (CSMWPLS) and searching combination moving window partial least squares (SCMWPLS) are proposed to search for an optimized spectral interval and an optimized combination of spectral regions from informative regions obtained by a previously proposed spectral interval selection method, moving window partial least squares (MWPLSR) [Anal. Chem. 74 (2002) 3555]. The utilization of informative regions aims to construct better PLS models than those based on the whole spectral points. The purpose of CSMWPLS and SCMWPLS is to optimize the informative regions and their combination to further improve the prediction ability of the PLS models. The results of their application to an open-path (OP)/FT-IR spectra data set show that the proposed methods, especially SCMWPLS can find out an optimized combination, with which one can improve, often significantly, the performance of the corresponding PLS model, in terms of low prediction error, root mean square error of prediction (RMSEP) with the reasonable latent variable (LVs) number, comparing with the results obtained using whole spectra or direct combination of informative regions for a compound. Regions consisting of the combinations obtained can easily be explained by the existence of IR absorption bands in those spectral regions. 相似文献
This article discusses problems of validating classification models especially in datasets where sample sizes are small and the number of variables is large. It describes the use of percentage correctly classified (%CC) as an indicator for success of a classification model. For small datasets, %CC should not be used uncritically and its interpretation depends on sample size. It illustrates the use of a common classification method, discriminant partial least squares (D-PLS) on a randomly generated dataset of 200 samples and 200 variables.
An aim of the classifier is to determine whether the null hypothesis (there is no distinction between two classes) can be rejected. Autoprediction gives an 84.5% CC. It is shown that, if there is variable selection, it must be performed independently on the training set to obtain a CC close to 50% on the test set; otherwise, over-optimistic and false conclusions can be reached about the ability to classify samples into groups.
Finally, two aims of determining the quality of a model are frequently confused, namely optimisation (often used to determine the most appropriate number of components in a model) and independent validation; to overcome this, the data should be split into three groups.
There are often difficulties with model building if validation and optimisation have been done on different groups of samples, especially using iterative methods, each group being modelled using properties, such as a different number of components or different variables. 相似文献
The densities of H2O, D2O, and MeOH solutions in acetonitrile with the solute concentrations up to 0.07 molar fractions at 278.15, 288.15, 298.15, 308.15, and 318.15 K were measured using vibrating-tube densimetry with an error 8·10–6 g cm–3. The limiting partial molar volumes for the H/D isotopomers of water and IaII in acetonitrile (V–2) and the isotope effects in V–2 and in excess molar volumes of acetonitrile—water mixtures were calculated. Molecules of H2O, D2O, and IaII form associates with acetonitrile molecules via hydrogen bonds. The associates have the packing volumes close to those in the individual solute. The water and methanol molecules were assumed to be incorporated into the acetonitrile structure without substantial changes in the latter. However, this process results in some compression of the system with a simultaneous increase in its expansibility. 相似文献
Using a precise technique of scanning microcalorimetry the heat capacity differences between water and dilute aqueous solutions of ethanol, n-propanol, n-butanol and n-pentanol were measured from 5 to 125°C and the partial molar heat capacities of these substances in water were determined. It was found that the heat capacity increment for alcohol disolved in water is proportional to the number of the-CH
2–
groups and decrease with a temperature increase. The heat capacity increment of hydration of non-polar groups is shown to be positive and large at room temperature and decreases in magnitude as the temperature increases. In contrast, the heat capacity increment of hydration of polar groups is negative at room tempreature and increases as the temperature increases. From the temperature dependence of the heat capacity increment one can assume that the water molecules solvated by the non-polar groups of the alcohols behave in a non-cooperative manner. 相似文献