Excess enthalpies of some 2-alkanone + 1-chloroalkane binary mixtures at 25 and 35°C

Excess molar enthalpies h^E at 25 and 35° C and atmospheric pressure, are reported for the binary mixtures formed by a 2-butanone and 2-pentanone with 1-chlorobutane, 1-chloropentane, 1-chlorohexane, or 1-chlorooctane. The h^E values for all the mixtures are positive, increasing as the 1-chloroalkane length increases and as the ketone length decreases. Excess molar enthalpies depend slightly on the temperature. The experimental values together with those from the literature were used to calculate the interaction parameters for the Dang-Tassios version of the UNIFAC model.Communicated at the Festsymposium celebrating Dr. Henry V. Kehiaian's 60^th birthday, Clermont-Ferrand, France, 17–18 May 1990.     

Thermodynamic properties of the ternary system MTBE+1-propanol+hexane

Experimental excess molar enthalpies and excess molar volumes of the ternary system x₁MTBE+x₂1-propanol+(1-x₁-x₂) hexane and the involved binary mixtures have been determined at 298.15 K and atmospheric pressure. Excess molar enthalpies were measured using a standard Calvet microcalorimeter, and excess molar volumes were determined from the densities of the pure liquids and mixtures, using a DMA 4500 Anton Paar densimeter. The UNIFAC group contribution model (in the versions of Larsen et al., and Gmehling et al.) has been employed to estimate excess enthalpies values. Several empirical expressions for estimating ternary properties from experimental binary results were applied.     

Microcalorimetric performance of the growth in culture of Escherichia coli,Proteus mirabilis and their mixtures in different proportions

Microcalorimetry is a technique that determines the heat flow produced as a result of microbial activities. The heat variations resulting from chemical reactions, which take place during metabolism, can be used to monitor bacterial growth in a culture medium. However, there are very few studies using calorimetry to investigate the relationships between two bacteria. In this work, we studied the interaction between E. coli and P. mirabilis, two bacteria belonging to the family Enterobacteriaceae. We have prepared three samples, mixing both enterobacteria at a concentration of 10³ CFU mL^?1 but in different proportions. Experimental equipment used was a Calvet microcalorimeter, where a constant temperature of 309.65 K was maintained. Then, we compared the shape of the heat flow–time curves of single microorganisms and their mixtures. Also, we calculated the thermokinetic parameters such as growth constant (k), generation time (G), detection time (t _d) and the amount of heat released (Q). The results obtained showed that when E. coli and P. mirabilis were put together in the culture medium, the growth profile of P. mirabilis seemed to dominate, even at low proportions in the sample.     

Estimation of the Nitta-Chao Parameters for the ether-group. Ether + n-alkane mixtures

In this work we have estimated the structural and interactional parameters of the ether- group for the group-contribution model of Nitta-Chao using a extensive experimental database of thermodynamic properties of ethers (monoethers, polyethers and acetals) and ether + n-alkane and ether + ether mixtures. The results obtained by Nitta-Chao model with this parameters get closer to the experimental values than those obtained with parameters of Eckart et al. (1986). The thermodynamic properties obtained by the Nitta-Chao model with old and new parameters were compared to predictions by other models such as Flory (1965) theory, DISQUAC (Kehiaian, 1977) model and UNIFAC model (versions of Dang and Tassios, 1986, and Larsen et al., 1987).     

Systematic evaluation of acetone and acetonitrile for use in hydrophilic interaction liquid chromatography coupled with electrospray ionization mass spectrometry of basic small molecules

Sub‐2‐µm particle size hydrophilic interaction liquid chromatography [HILIC] combined with mass spectrometry has been increasing in popularity as a complementary technique to reversed‐phase LC for the analysis of polar analytes. The organic‐rich mobile phase associated with HILIC techniques provides increases in compound ionization, due to increased desolvation efficiency during electrospray ionisation mass spectrometric (ESI‐MS) analysis. Although recent publications illustrated selectivity and response comparisons between reversed‐phase LC/MS and HILIC LC/MS, there are limited discussions evaluating the optimisation of the mass spectrometry parameters regarding analytes and alternative mobile phases. The use of acetone as an alternative organic modifier in HILIC has been investigated with respect to signal‐to‐noise in ESI‐MS for a variety of polar analytes. Analyte reponses were measured based on a variety of cone and capillary voltages at low and high pH in both acetone and acetonitrile. In order to visualise compound behaviour in the ESI source, surface plots were constructed to assist in interpreting the observed results. The use of acetone in ESI is complicated at low m/z due to the formation of condensation products. Favourable responses were observed for certain analytes and we envisage offering an insight into the use of acetone as an alternative to acetonitrile under certain analytical conditions for particular compound classifications for small molecule analysis. We also highlight the importance of optimising source voltages in order to obtain the maximum signal stability and sensitivity, which are invariably, highly solvent composition dependent parameters. Copyright © 2011 John Wiley & Sons, Ltd.     

Thermophysical properties for (diethyl carbonate + p-xylene + octane) ternary system

The density and speed of sound of the ternary mixture (diethyl carbonate + p-xylene + octane) have been measured at atmospheric pressure and in the temperature range T = (288.15 to 308.15) K. Besides, surface tension has been also determined for the same mixture at T = 298.15 K. The experimental measurements have allowed the calculation of the corresponding derived properties: excess molar volumes, excess isentropic compressibilities, and surface tension deviations. Excess properties have been correlated using Nagata and Tamura equation and correlation for the surface tension deviation has been done with the Cibulka equation. Good accuracy has been obtained. Based on the variations of the derived properties values with composition, a qualitative discussion about the intermolecular interactions was drawn.     

Excess enthalpies of ternary mixture consisting of tert-butyl methyl ether, ethanol and heptane

Excess molar enthalpies, measured at 298.15 K in a Calvet microcalorimeter, are reported for {x ₁ tert-butyl methyl ether (MTBE)+x ₂ethanol (EtOH)+(1?x ₁?x ₂)heptane}. Smooth representations of the results are presented and used to construct contant excess molar enthalpy contours on Roozeboom diagrams.     

Assessment of Polygonum capitatum Buch.‐Ham. ex D.Don by metabolomics based on gas chromatography with mass spectrometry

Polygonum capitatum is widely used in southwest China. It has considerable therapeutic efficacy for urinary tract infections. P. capitatum contains multiple components and quality assessment can be achieved by means of metabolic fingerprinting. In this paper, a new strategy for P. capitatum quality determination was developed. Eleven batches of P. capitatum were collected from five geographical areas in China including a standard batch regulated by Good Agriculture Practice. Gas chromatography with mass spectrometry was used to generate fingerprints from triplicate extractions to each batch (n = 33). Hierarchical clustering analysis was applied to assess similarities among the ten batches to the standard batches. Orthogonal projection to latent structures discriminate analysis, cross‐validated with permutation tests, was performed to investigate discriminating metabolites. Results demonstrated that the overall evaluation hierarchical clustering analysis clustered two batches with distance > 3. Orthogonal projection to latent structures discriminate analysis (R²Y (cum) = 0.997, Q² (cum) = 0.97, CV‐ANOVA = 8.48 × 10^?11) indicated that several sugars contributed to batch classification. This method is a rational approach that can classify against a regulated plant standard and distinguishes samples from different origins or processing time in a holistic manner and metabolites driving any differences can be easily identified.     

Analysis of the intramolecular proximity effect on dichloroalkane + alkane mixtures using Nitta-Chao model

Literature data for vapor liquid equilibria, activity coefficients at infinite dilution, enthalpies of mixing, volumes of mixing of ,ω-dichloroalkane (ClCH₂---(CH₂)_m−2---CH₂Cl, from M=1 to 6) + − alkane mixtures together with vaporization enthalpies and molar volumes of pure dichloroalkanes were examined on the basis of the Nitta-Chao model. In this paper structure-dependent interaction energetic coefficients for this model were presented for a first time. According to the proximity effect when the two chloro groups of the chloroalkane are more separated they become independent and the reported values of the energetic parameters approach to these of the 1-chloroalkane. Similar trends were reported previously for several authors in the framework of the DISQUAC model. A comparison with the predictions of DISQUAC and UNIFAC (version of Larsen et al.) is presented.