Analytical and numerical studies for Seiches in a closed basin with bottom friction

A standing wave oscillation in a closed basin, known as a seiche, could cause destruction when its period matches the period of another wave generated by external forces such as wind, quakes, or abrupt changes in atmospheric pressure. It is due to the resonance phenomena that allow waves to have higher amplitude and greater energy, resulting in damages around the area. One condition that might restrict the resonance from occurring is when the bottom friction is present. Therefore, a modified mathematical model based on the shallow water equations will be used in this paper to investigate resonance phenomena in closed basins and to analyze the effects of bottom friction on the phenomena. The study will be conducted for several closed basin shapes. The model will be solved analytically and numerically in order to determine the natural resonant period of the basin, which is the period that can generate a resonance. The computational scheme proposed to solve the model is developed using the staggered grid finite volume method. The numerical scheme will be validated by comparing its results with the analytical solutions. As a result of the comparison, a rather excellent compatibility between the two results is achieved. Furthermore, the impacts that the friction coefficient has on the resonance phenomena are evaluated. It is observed that in the prevention of resonances, the bottom friction provides the best performance in the rectangular type while functioning the least efficient in the triangular basin. In addition, non-linearity effect as one of other factors that provide wave restriction is also considered and studied to compare its effect with the bottom friction effect on preventing resonance.     

Photoelectrochemical cells using metal-decorated carbon nanotube electrodes

We fabricated the photoelectrochemical (PEC) cells using n-type TiO₂ and metal (Pt, Pd)-decorated carbon nanotubes (CNTs) as an anode and a cathode, respectively. Photovoltaic effects were clearly observed. Compared with conventional PEC cell with Pt cathode, a larger photo-voltage was found in the PEC cells with the metal-decorated CNT cathode due to p-type semiconducting properties of CNTs. Additionally, we connected two PEC cells in series to decompose water into oxygen and hydrogen. Indeed, the connected PEC cells yielded the photo-voltage of about 1.35 V, which is larger than 1.23 V required for water splitting. This result demonstrates the possibility of hydrogen generation using the connected PEC cells without an external bias.     

Solubility and Raman Spectroscopic Study of As(III) Speciation in Organic Compound-Water Solutions. A Hydration Approach for Aqueous Arsenic in Complex Solutions

Solubilities of arsenolite (As₂O₃, cub.) were measured from 22 to 90°C in water–acetone, water–acetic acid, and water—formic acid solutions of compositions ranging from the pure organic compound to pure water. Raman spectra were obtained at ambient temperature on As-containing water–acetic acid and water–acetone solutions. Results show that arsenic solvation by these organic compounds is negligible and hydroxide species dominate As speciation over a wide range of water activity (a_{H 2 O}> 0.01). The solubility data were analyzed using an approach based on stoichiometric hydration reactions. Results show that As₂O₃ solubility can be described as a function of water activity, independently of the nature of the organic compound, by involving two neutral As hydroxide complexes: As(OH)₃ and As(OH)₃·4H₂O. Stability constants derived for these species indicate that hydration weakens with increasing temperature. Calculations using these constants show that at low temperatures the tetrahydrate As(OH)₃·4H₂O is dominant in water-rich solutions; by contrast, in high-temperature crustal fluids, As(OH)₃ becomes the major As species. The proposed hydration model can be used to analyze solubility of arsenic-bearing minerals and arsenic transport in complex H₂O–CO₂—electrolyte solutions encountered in natural and industrial environments.     

Refratometric study of ternary mixtures formed by water,glucose and acetonitrile at temperatures ranging from 293 K to 333 K

The study of thermodynamic properties of solutions provides important information on existing molecular interactions between the components present in a solution. These studies are critical for testing, validation and development of theories and mathematical models. The refractometric study of a solution is a simple assessment that can contribute to the understanding of these interactions. In this context, the behaviour of the binary water and glucose mixture was studied as well as ternary mixtures of water, glucose and acetonitrile at five different temperatures in the range 293–333 K by the determination of the refractive index of the solution. Due to the weakening of the molecular interactions with the increasing of the temperature, a decreasing dependence of refractive index with temperature was observed. The addition of acetonitrile provides an increase in the refractive index indicating the formation of clusters in the solution.     

Mechanistic insights on DBU catalyzed β‐amination of nbs to chalcone driving by water: Multiple roles of water

DFT calculations were conducted to pursue deeper understandings on the mechanism and the explicit role of trace water in the DBU‐catalyzed β‐amination of NBS to chalcone. Being different from previously proposed by Liang et al., a cooperative participation of both DBU and water is noticed in the preferred mechanism. The preferential mechanistic scenario assisted by water undergoes three major steps: the formation of succinimide and HBrO, concerted nucleophilic addition and H‐shift, and keto‐enol tautomerization. Moreover, we found that DBU‐HBrO is unnecessary in the third step and three‐water‐cluster assisted keto‐enol tautomerization is the most advantageous case. It is further noted that the catalytic position of the third water molecule and the proton shift orientation to some extent affect step 3 via O···H O and O H···π interactions, which is confirmed by AIM analysis. The computational results suggest that water molecules play pivotal roles as reactant, catalyst, and stabilizer to promote the reaction of chalcone and NBS. The origin of the more stable transition state structure in the rate‐determining step of DBU‐water catalyzed mechanism is ascribed to noncovalent interactions, halogen bond, and electrostatic interactions than DBU only ones. © 2017 Wiley Periodicals, Inc.     

Directly‐coupled‐column ultra‐fast liquid chromatography with diode array detection method for the rapid quantification of allergenic disperse dyes in water preconcentrated by magnetic solid‐phase extraction

A directly‐coupled‐column ultra‐fast liquid chromatography coupled with diode array detection method for the determination of 12 allergenic disperse dyes in river water at sub‐ppb levels has been developed and successfully validated. The analytical method is based on the use of two different reversed‐phased columns connected through a two‐position switching valve. A baseline separation was achieved by proper selection of stationary phases, mobile phases, and the use of a gradient elution in both dimensions. Furthermore, an easy‐to‐handle magnetic solid‐phase extraction procedure was developed for the preconcentration of 12 allergenic disperse dyes from river water. An enrichment factor of 100 times was obtained. The results showed excellent performance in terms of trueness (76.8–99.0%), precision (intraday: 2.2–8.0%, interday: 3.3–8.2%), and sensitivity (limits of determination, 0.027–1.46 μg/L). Twenty real samples collected from the outfalls in the Yaojiang, Yongjiang and Fenghuajiang estuary were analyzed, and three of the studied compounds were found in one collected sample (12.6 μg/L for disperse blue 7, 11.6 μg/L for disperse blue 106, and 0.22 μg/L for disperse blue 3).     

Influence of the nature of membrane ionogenic groups on water dissociation and electrolyte ion transport: A rotating membrane disk study

Polarization properties of electromembrane systems (EMS) consisting of a heterogeneous membrane, either the MK-41 phosphonic acid membrane or the MK-40 sulfonic acid membrane, and dilute sodium chloride solutions are investigated with the rotating membrane disk method. For the MK-41/0.01 M NaCl and MK-41/0.001 M NaCl EMS, effective ion transport numbers and partial current-voltage curves (CVC) are measured for sodium and hydrogen ions, and limiting-current densities and the diffusion-layer thickness are calculated as functions of the rotation rate of the membrane disk. With the theory of the overlimiting state of EMS, internal parameters of the systems under investigation—the diffusion-layer thickness, the space-charge distribution, and electric-field strengths in the diffusion layer and in the membrane—are calculated from experimentally obtained CVC and the dependence of effective transport numbers on current density. The catalytic influence of ionogenic groups on the dissociation rate of water is analyzed quantitatively. Partial CVC for H⁺ ions are calculated for the space-charge region in MK-40 and MK-41 membranes. Analogous CVC for bipolar membranes containing sulfonic acid and phosphonic acid groups are compared. The dissociation mechanism of water is the same in all EMS and is independent of the membrane type and the nature of the functional groups.     

Kinetic study for liquefaction of tar in sub- and supercritical water

Liquefaction of tar from oil distillation was studied under sub- and supercritical water conditions using a batch reactor at 623 and 673 K and 25-40 MPa. The reaction scheme for tar liquefaction was determined as follows: the liquefaction process of tar occurs first and then intermediate chemical compounds are transformed into lighter molecular weight species. The effects of pressure and treatment time were combined into a single severity parameter that was used to monitor the conversion of tar. The main products from the liquefaction of tar were phenol (3.44 wt%), biphenyl (2.23 wt%), diphenylether (13.70 wt%) and diphenylmethane (1.30 wt%), respectively. Liquefaction of tar clearly increased with increasing water density at the same temperature reaction. It indicates that hydrolysis was important in the cleavage of the macromolecular structure of tar under sub- and supercritical conditions. Based on the results, this method could become an efficient method for tar liquefaction, producing high yields of valuable chemical intermediates.     

Efficient free energy calculation of water across lipid membranes

An efficient free energy (FE) calculation of a water molecule to go across lipid membranes is presented. Both overlapping distribution and cavity insertion Widom methods are complementarily used. The former is useful for a dense region where water molecules are found, i.e., from the interfacial to bulk water region, while the latter works well in the low density region, i.e., the hydrocarbon region. Since both methods evaluate the excess chemical potential of water, the obtained FE profile is free from the fitting problem usually arisen when a FE difference method is used. A diphytanyl phosphatidylcholine bilayer is used for our test calculations. An excellent and fast convergence of the chemical potential is obtained when each method is applied for the appropriate region. The estimated FE barrier using the Ewald method for the electrostatic interaction is approximately 7.2 kcal/mol, which is higher than that using the interaction cutoff of 20 A by about 0.9 kcal/mol.     

Freezing and Melting of Water Confined in Silica Nanopores

In nanosized pores, liquid water can be thermodynamically stable down to temperatures well below the limit of homogeneous nucleation of bulk water (～235 K). Studies of water in such pores therefore offer an opportunity to reveal the anomalous behavior of deeply supercooled water. Herein we focus on recent studies of the limits of freezing and melting of water in the cylindrical pores of ordered mesoporous silicas with pore diameters in the range of 2–10 nm, based on vapor sorption measurements, calorimetric studies, NMR spectroscopy and cryoporometry, and neutron diffraction studies.