MNDO and DFT Computational Study on the Mechanism of the Oxidation of 1,2-Diphenylhydrazine by Iodine

The reaction mechanisms of the oxidation of 1,2-diphenylhydrazine by iodine have been examined using semiempirical and density functional theory methods, the oxidation proceeded via two independent pathways that can be separately monitored. One pathway involved the chain multistep mechanism. The other pathway occurred via a one-step mechanism in which a “cyclic” activated complex was formed which on disproportionation gave the products. The one-step “cyclic” activated complex mechanism proceeds more rapidly than the chain multistep mechanism. The results were explained by analyses based on computational energetics of the optimised reactants, intermediates, transition states, and products of the reaction of iodine with 1,2-diphenylhydrazine.

Perborate Oxidation of Substituted 5-Oxoacids in Aqueous Acetic Acid Medium: A Kinetic and Mechanistic Study

Kinetics and mechanism of oxidation of substituted 5-oxoacids by sodium perborate in aqueous acetic acid medium have been studied. The reaction exhibits first order both in [perborate] and [5-oxoacid] and second order in [H+]. Variation in ionic strength has no effect on the reaction rate, while the reaction rates are enhanced on lowering the dielectric constant of the reaction medium. Electron releasing substituents in the aromatic ring accelerate the reaction rate and electron withdrawing substituents retard the reaction. The order of reactivity among the studied 5-oxoacids is p-methoxy ≫ p-methyl > p-phenyl > –H > p-chloro > p-bromo > m-nitro. The oxidation is faster than H2O2 oxidation. The formation of H2BO3+ is the reactive species of perborate in the acid medium. Activation parameters have been evaluated using Arrhenius and Eyring’s plots. A mechanism consistent with the observed kinetic data has been proposed and discussed. Based on the mechanism a suitable rate law is derived.

Adsorption of Brilliant Green onto Luffa Cylindrical Sponge: Equilibrium, Kinetics, and Thermodynamic Studies

The sponge of Luffa cylindrical (LFC), a fibrous material, was employed as adsorbent for the removal of Brilliant Green (BGD) from aqueous effluent via batch studies. The optimum removal of BGD was found at pH 8.2 and the equilibrium was attained within 3 hours. The kinetic data are analyzed using several models including pseudo-first-order, pseudo-second-order, power function, simple elovich, intraparticle diffusion, and liquid film diffusion. The fitting of the different kinetics models to the experimental data, tested by error analysis, using the linear correlation coefficient r2 and chi-square analysis χ2, showed that the mechanism of adsorption process was better described by pseudo-second-order and power function kinetic models. The equilibrium isotherm data were analyzed using Langmuir, Freundlich, and Temkin models and the sorption process was described by the Langmuir isotherm with maximum monolayer adsorption capacity of 18.2 mg/g at 303 K. The thermodynamic properties ΔG0, ΔH0, and ΔS0 showed that adsorption of BGD onto LFC was spontaneous, endothermic, and feasible within the temperature range of 303–313 K.

Volumetric Properties of Aqueous Solutions of Ethylene Glycols in the Temperature Range of 293.15–318.15 K

Densities of aqueous solutions of Ethylene glycol (EG), diethylene glycol (DEG), and triethylene glycol (TEG) were measured at temperatures from 293.15 to 318.15 K and molalities ranging from 0.0488 to 0.5288 mol·kg−1. Volumes of all investigated solutions at a definite temperature were linearly dependent on the solute molality; from this dependence the partial molar volumes at infinite dilution were determined for all solutes. It was found that the partial molar volumes at infinite dilution V-2,0 were concentration independent and slightly increase with increasing temperature. The partial molar volumes at infinite dilution V-2,0 or the limiting apparent molar volumes of ethylene glycols were fitted to a linear equation with the number of oxyethylene groups (n) in the solute molecule. From this equation a constant contribution of the terminal (OH) and the (CH2CH2O) groups to the volumetric properties was obtained. The thermal expansion coefficient (α1,2) for all investigated solutions was calculated at temperatures from 293.15 to 318.15 K. The thermal expansion coefficients for all solutes increase with increasing temperature and molality. Values of (α1,2) were higher than the value of the thermal expansion coefficient of the pure water.

Sol-Gel Synthesized Semiconductor Oxides in Photocatalytic Degradation of Phenol

Effectiveness of photocatalytic degradation of phenol in aqueous solution using semiconductor oxides (SO) prepared by a sol-gel method was examined. The physical and chemical properties of synthesized catalysts were investigated by X-ray diffraction (XRD), diffuse reflectance UV-Vis spectroscopy (DRS), and N2-adsorption measurements. The optimal conditions of the photocatalytic degradation of phenol using prepared titanium dioxide sample were defined.

A Quantum Chemical Study on Structures and Electronic (Hyper)polarizabilities of 2,2′-Biselenophene Rotamers

Geometries, IR and Raman spectra, nucleus independent chemical shifts, and static electronic (hyper)polarizabilities of the equilibrium conformations of 2,2′-biselenophene were determined in vacuum using density functional theory (DFT) computations. At the DFT-PBE0/6-31G+pdd′ level the antigauche structure characterized by the Se-C2-C2′-Se dihedral angle of 157° is the global minimum, whereas the syngauche rotamer (Se-C2-C2′-Se = 40°) lies ca. 0.7 kcal·mol−1 above the antigauche form. The structural and spectroscopic properties as well as the electronic polarizability of the antigauche are similar to those of the syngauche structure. On the other hand, the dipole moments and first-order hyperpolarizabilities are strongly influenced by the conformational characteristics, increasing by ca. a factor of five when passing from the antigauche to the syngauche form.

Inefficient Vibrational Cooling of C60 in a Supersonic Expansion

High-resolution gas-phase infrared spectroscopy of buckminsterfullerene (C60) was attempted near 8.5 μm using cavity ring-down spectroscopy. Solid C60 was heated in a high-temperature (~950 K) oven and cooled using an argon supersonic expansion generated from a 12.7 mm × 150 μm slit. The expected S/N ratio is ~140 for vibrationally cold C60, but no absorption signal has been observed, presumably due to a lack of vibrational cooling of C60 in the expansion. Measurements of D2O at 875 K are presented as a test of instrument alignment at high temperature and show that efficient rotational cooling of D2O occurs in the hot oven (Trot = 20 K in the expansion), though vibrational cooling does not occur. The attempted C60 spectroscopy is compared to previous work which showed efficient vibrational cooling of polycyclic aromatic hydrocarbons (PAHs). Possible alternative experiments for observing a cold, gas-phase spectrum of C60 are also considered.

Thermophysical Properties of Binary Liquid Systems of Ethanoic Acid, Propanoic Acid, and Butanoic Acid with Benzene or Acetophenone

The density (), viscosity (), and surface tension () of binary mixtures of carboxylic acids (CAs) (ethanoic acid (EA), propanoic acid (PA), butanoic acid (BA)) + benzene (BEN) or acetophenone (ACT) have been measured at 298.15, 308.15, and 318.15 K. From the experimental results, excess values of molar volume (), viscosity (), Gibb's free energy for the activation of low (), and surface tension () were evaluated and fitted to a Redlich-Kister type of equation. The parameter “” of Grunberg and Nissan expression has also been calculated. From the sign and magnitude of , , , , and “” values, it is concluded that specific interactions are present in CA+ACT system and these interactions are absent in CA + BEN mixtures. Various viscosity and surface tension models have been used to test the consistency of the data.

Surface Characterization of Phenylpropanolamine Drug by Inverse Gas Chromatography

The surface thermodynamic properties can be used to understand the interactive potential of a drug surface with a solid or liquid excipient during its formulation and drug release process. The retention data were measured for n-alkanes and polar solutes at intervals of 5 K in the temperature range 318.15–333.15 K by Inverse Gas Chromatography (IGC) on the solid surface of phenylpropanolamine (PPA) drug. The retention data were used to evaluate the dispersive surface free energy, γSd, and Lewis acid-base parameters, Ka and Kb, for the PPA drug. The values, γSd, were decreasing linearly with increase of temperature and at 323.15 K the value was found to be 26.01±0.40 mJ/m2. The specific components of enthalpy of adsorption of polar solutes have been applied to evaluate Lewis acid-base parameters. The Ka and Kb values were found to be 0.451±0.033 and 0.824±0.622, respectively, which suggests that the PPA surface contains more basic sites and interact strongly in the acidic environment.

Equilibrium, Kinetics, and Thermodynamics of the Biosorption of Zn(II) from Aqueous Solution Using Powdered Cow Hooves

The capability of cow hoof (CH) to remove Zn(II) from aqueous solution under the influence of sorbent size, solution pH, contact time, and sorbent dosage was investigated through batch studies. Equilibrium studies were conducted at three different temperatures (298, 308, and 318 K) by contacting different concentrations of Zn(II) solution with a known weight of cow hoof. The biosorption of Zn onto cow hoof was found to increase with increase in the mass of sorbent used while the biosorption efficiency was found to decrease with increase in sorbent particle size. The optimum conditions of pH 4 and contact time of 60 minutes were required for maximum removal of Zn(II) by cow hoof (mesh size 212 µm). The equilibrium data were modelled using Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherm models. The data were best fitted by Langmuir model. The kinetic data were analysed using Lagergren kinetic equations and these were well fitted by the pseudo-second-order kinetic model. The thermodynamic parameters showed that the biosorption process was feasible, spontaneous, and endothermic.