Re-evaluation of Activity Coefficients in Dilute Aqueous Hydrobromic and Hydriodic Acid Solutions at Temperatures from 0 to 60 °C

Simple two-parameter Hückel equations can be used for the calculation of the activity coefficients in aqueous hydrobromic and hydriodic acid solutions at temperatures from 0 to 60 °C and from 0 to 50 °C, respectively, at least up to a molality of 0.5 mol·kg^?1. The data measured by Macaskill and Bates (J. Solution Chem. 12:607–619, 1983) at 25 °C and those measured by Hetzer et al. (J. Phys. Chem. 68:1929–1933, 1964) at various temperatures on galvanic cells without a liquid junction were used in the parameter estimations for the hydrogen bromide (HBr) and hydrogen iodide (HI) solutions, respectively. The latter data consist of sets from 0 to 50 °C at intervals of 5 °C. The parameter values for HBr solutions were also tested using the numerous galvanic cell points from the other three data sets existing in the literature for hydrobromic acid solutions and covering wide range of temperatures from 0 to 60 °C. It was observed in the parameter estimations and tests that all of the estimated parameters are independent of the temperature. The recommended parameter values were additionally tested using the isopiestic data of Macaskill and Bates (see the citation above) and those of Harned and Robinson (Trans. Faraday Soc. 37:302–307, 1941) for dilute HBr and HI solutions at 25 °C, respectively. In more concentrated solutions up to a HBr molality of 4.5 mol·kg^?1 and up to a HI molality of 3.0 mol·kg^?1, an extended Hückel equation was used, which contains an additional quadratic term with respect to the molality. The parameters for the extended Hückel equations were determined from these isopiestic data and tested using these data and the existing galvanic cell data. The activity and osmotic coefficients calculated from the resulting equations are recommended in the present study for the more concentrated solutions. The recommended values are compared to the activity values reported in several previous tabulations.     

Proximity effects of oxygen atoms on the enthalpies of formation of simple diethers: a computational G3(MP2)//B3 study

The enthalpies of formation of a number of acyclic, straight‐chain ethers and diethers were determined by G3(MP2)//B3 calculations. The principal aim of the work was to study the magnitude of the O…O proximity effect on the enthalpy contents of diethers as a function of the distance (number of bonds) between the O atoms. 1,4‐Diethers and 1,5‐diethers were computed to be destabilized by ca. 4.5 (±0.5) and 3.2 (±0.4) kJ mol^?1, respectively, by the O…O proximity effect. The effect was calculated to be negligible in diethers with the O atoms in positions more remote than 1,5 from each other, whereas 1,3‐diethers (acetals) are stabilized by ca. 22 kJ mol^?1, likely on account of the anomeric effect. Calculations on simple monoethers show that the contributions to of CH₂ groups in the β and γ positions (relative to O) are reduced by ca. 0.8 and 0.3 kJ mol^?1, respectively, relative to those of CH₂ groups more remote from the O atom. The computational enthalpies of formation of the studied monoethers and diethers, both cyclic and acyclic, are generally in good agreement with experimental data, another important result of the present work. Copyright © 2008 John Wiley & Sons, Ltd.     

Highly Transparent and Mechanically Robust Energy-harvestable Piezocomposite with Embedded 1D P(VDF-TrFE) Nanofibers and Single-walled Carbon Nanotubes

Herein, highly transparent, flexible, and ultrathin piezocomposite, in which electrospun poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)] nanofibers (NFs) and aerosol-synthesized single-walled carbon nanotubes (SWCNTs) are embedded in elastomer matrix, is fabricated. The P(VDF-TrFE) NF mat is exploited as a piezoelectric layer of the piezocomposite while the SWCNT film is applied as a transparent conductive electrode thereof. The use of these 1D nanomaterials allows the piezocomposite not only to be high transparency along with low diffusion of light (i.e., haze factor) but also to exhibit enhanced mechanical properties. In addition, the coupling effect of piezo- and flexoelectricity exhibited from the electrospun NFs and the acid-doping effect conducted on the SWCNTs facilitates a significant improvement in kinetic energy-harvesting performance, leading to a maximum output voltage of 26.8 V. Moreover, electrospinning and aerosol chemical vapor deposition methods employed here are facile, scalable, and cost-effective, thus are expected to accelerate the development of industrially feasible next-generation wearable electronics.