Separation of polar and steric effects in the oxidation of ortho-substituted benzaldehydes by N-bromobenzamide

The kinetics of the oxidation of twelve ortho-substituted benzaldehydes by N-bromobenzamide (NBB) to the corresponding benzoic acids have been studied. The reaction is first order with respect to NBB, the aldehyde and hydrogen ions. The addition of benzamide has no effect on the reaction rate. (PhCONH₂Br)⁺ has been postulated as the reactive oxidising species. The correlation of rates with the single substituent-parameter equations is poor. The correlation with Charton’s equation of inductive, resonance and steric parameters is satisfactory. However, excellent correlations were obtained, when Charton’s steric parameter was used along with Taft’s σ₁; andσ _R ⁺ substituent constants. The polar reaction constants have negative values. The reaction is subject to steric hindrance by the ortho-substituents.     

Kinetics and mechanism of the oxidation of some α‐hydroxy acids by tetrachloroaurate(III) in acetic acid‐sodium acetate buffer medium

The kinetics of oxidation of some neutralized α‐hydroxy compounds such as glycolic (GA), lactic (LA), α‐hydroxyisobutyric(IB), mandelic (MA), atrolactic (AL), and benzilic (BA) acids by tetrachloroaurate(III) have been studied. The substrates are oxidized to give formaldehyde, acetaldehyde, acetone, benzaldehyde, acetophenone, and benzophenone for the respective reactions. The rate of the reaction increases with increasing [substrate] and pH but decreases with increase in [Cl⁻¹]. Temperature influence is quite marked in all these reactions. A mechanism involving the formation of an unstable complex, which decomposes to give the respective reaction products, is proposed. The reactivity of the α‐hydroxy acids towards gold(III) are as follows: AL > MA > BA > IB > LA > GA. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 873–882, 1999     

Correlation analysis of structure and reactivity in the oxidation of substituted benzyl alcohols by bis(2,2′-bipyridyl) copper(II) permanganate

The oxidation of substituted benzyl alcohols by bis(2,2′-bipyridyl) copper(II) permanganate (BBCP), leading to the corresponding benzaldehydes is first-order with respect to BBCP. Michaelis-Menten type kinetics were observed with respect to the alcohols. The oxidation of a,a-dideuteriobenzyl alcohol indicated the presence of a substantial kinetic isotope effect. The rates of oxidation of meta- and para-substituted benzyl alcohols were correlated in terms of Charton's triparametric LDR equation whereas ortho- substituted benzyl alcohols were correlated with a four parametric LDRS equation. The results of correlation analyses point to an electron-deficient reaction center in the transition state. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 9–16, 1997.     

Kinetics and mechanism of the oxidation of glycolaldehyde by tetrachloroaurate(III)

The kinetics of the reaction between glycolaldehyde (GA) and tetrachloroaurate(III) in acetic acid-sodium acetate buffer has been studied. The reaction is first-order with respect to [Au^III] as well as [GA]. Both H⁺ and Cl⁻ ions retard the rate of reaction. AuCl₄⁻, AuCl₃(OH₂), and AuCl₃(OH)⁻ are the reactive species of gold(III) with gradually increasing reactivity. A reaction mechanism involving two-electron transfer rate determining steps has been proposed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 613–619, 1998     

Kinetics and Mechanism of the Oxidation of Some Thioacids by Hexamethylenetetramine-Bromine

Oxidation of thioacids by hexamethylenetetramine-bromine proceeds through an intermediate complex in the pre-equilibrium and its subsequent decomposition in the slow step.     

Hilbert Modules and Stochastic Dilation of a Quantum Dynamical Semigroup on a von Neumann Algebra

A general theory for constructing a weak Markov dilation of a uniformly continuous quantum dynamical semigroup T _t on a von Neumann algebra ? with respect to the Fock filtration is developed with the aid of a coordinate-free quantum stochastic calculus. Starting with the structure of the generator of T _t , existence of canonical structure maps (in the sense of Evans and Hudson) is deduced and a quantum stochastic dilation of T _t is obtained through solving a canonical flow equation for maps on the right Fock module ?⊗Γ(L ²(ℝ₊,k ₀)), where k ₀ is some Hilbert space arising from a representation of ?^′. This gives rise to a *-homomorphism j _t of ?. Moreover, it is shown that every such flow is implemented by a partial isometry-valued process. This leads to a natural construction of a weak Markov process (in the sense of [B-P]) with respect to Fock filtration. Received: 15 June 1998/ Accepted: 4 March 1999     

Study on the Existence of Hydrogen Bonds in Ammonium Permanganate

The crystal structures of ammonium permanganate and ammonium perchlorate at 293 K were determined and compared. X‐ray and vibrational spectroscopic data confirmed the existence of weak hydrogen bonds in NH₄MnO₄. These hydrogen bonds proved to be slightly stronger than H‐bonds in ammonium perchlorate. Difference between the results of diffuse reflectance and KBr matrix pellet IR spectra of NH₄MnO₄ has been explained.     

Enhanced Photocatalytic Performance of rGO Modulated β-Ga2O3 for Wastewater Treatment

Rapid urbanization has inevitably raised challenges by indirectly adding industry waste to the environment. This problem becomes even more severe when contamination of consumable water is considered. As a leading sector in semiconductor-related research to face such challenges, gallium oxide and its derivatives have shown remarkable performance by exhibiting controlled, recyclable photocatalytic activities. This work demonstrates the enhancement of the photocatalytic performance of β-Ga₂O₃, which is related to the structural and morphological variation induced by rGO wrapping. Firstly, the Ga₂O₃ nanostructures are obtained by calcinating gallium oxide hydroxide (GaOOH), which is synthesized via a simple chemical route. On the other hand, rGO wrapped β-Ga₂O₃ is synthesized using in-situ hydrothermal treatment. In addition to traditional characterizations such as X-ray diffractometry (XRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, etc., the photocatalytic performance of both pristine and composite systems is studied by time-dependent UV–Vis absorption spectrum for the degradation of different organic toxic pollutants. It is observed that the composite sample exhibited a larger effective surface area and enhanced optical absorption in the UV–Vis range as compared to the pristine gallium oxide sample. Under UV light irradiation, the rGO wrapped β-Ga₂O₃ nanobars can degrade rhodamine B dye entirely within 25 min and exhibit a higher photodegradation rate of 0.1598 min⁻¹ which became 3.5 times higher as compared to that of pure gallium oxide.     

Higher-order solution for dust acoustic solitary waves in an unmagnetized dusty plasma

The effect of higher-order nonlinearity on dust acoustic solitary waves is studied taking into account the dust-charge variation. The model of charge fluctuation, taken here, is of the formI _e+I _i=0,I _e andI _i being the electronic and ionic currents. The dust charge is determined self consistently from the current-balance equation. It is found that the higher-order correction modifies the amplitude and width of the dust acoustic solitary waves. The effect of dust-charge streaming is also discussed.     

Relative scattering and time delay in presence of a uniform electric field

Relative scattering is studied in the presence of a uniform field. It is shown that as the field strength tends to zero, the time delay tends to the time delay of the system without the field.