Sharif Digital Repository

Rate constants, kA. for the aromatic nucleophilic substitution reaction of 2-chloro-3,5-dinitropyridine with aniline were determined in different compositions of 1-(1-butyl)-3-methylimidazolium terafluoroborate ([bmim]BF4) mixed with water, methanol, and ethanol at 25°C. The obtained rate constants of the reaction in pure solvents are in the following order: water > methanol > ethanol > [bmim]BF4. In these solutions, rate constants of the reaction decrease with the mole fraction of the ionic liquid. Single-parameter correlations of log kA versus normalized polarity parameter (ETN), hydrogen bond acceptor basicity (β), hydrogen bond donor acidity (α), and dipolarity/polarizability (π*) do not... 

The 1H-13C coupling constants of methyl α- and β-pyranosides of d-glucose and d-galactose have been measured by one-dimensional and two-dimensional 1H-13C heteronuclear zero and double quantum, phase sensitive J-HMBC spectra to determine a complete set of coupling constants (1JCH, 2JCH, 3JCH, 2JHH, and 3JHH) within the exocyclic hydroxymethyl group (CH2OH) for each compound. In parallel with these experimental studies, structure, energy, and potential energy surfaces of the hydroxymethyl group for these compounds were determined employing quantum mechanical calculations at the B3LYP level using the 6-311++G** basis set. Values of the vicinal coupling constants involving 1H and 13C in the... 

The mechanism and kinetics of the hydrogen evolution reaction (HER) on tin electrode in 0.1 M H2SO4 solution were studied using the methods of steady-state polarization and electrochemical impedance spectroscopy. The simulation of the data obtained from these two methods, using nonlinear fitting procedure allowed us to determine the rate constants of Volmer, Heyrovsky and Tafel steps associated with the mentioned reaction. The kinetic results indicate that HER mechanism at low negative potentials is a serial combination of Volmer step and parallel Tafel and Heyrovsky steps. At high negative potentials where the hydrogen coverage reaches its limiting value, a Tafel line with the slope of -... 

Electrocatalytic activity of electrodeposited nanocrystalline CoNiFe alloy in hydrogen evolution reaction (HER) was studied in 1 M NaOH solution. The steady-state polarization measurement and electrochemical impedance spectroscopy were used to determine the Tafel slope, the exchange current density and the activation energy. The simulation of the data obtained from these two methods, using a nonlinear fitting procedure, allowed us to determine the surface coverage and the rate constants associated with the mentioned reaction. The ac-impedance spectra measured at various overpotentials in the HER region exhibited three semicircles in the complex plane plots. The high-frequency semicircle was... 

Aromatic nucleophilic substitution reaction kinetics of 2-chloro-3,5-dinitropyridine with aniline was studied in aqueous solutions of methanol, ethanol, and 2-propanol at room temperature. The obtained results for aqueous solutions indicate that the second-order rate constants are in order of 2-propanol>ethanol>methanol with a maximum at water mole fraction of 0.9. The influence of solvent parameters including normalized polarity (E TN), dipolarity/polarisability (π*), and hydrogen bond donor acidity (α) on the second-order rate constants were investigated and multiple regressions gave much better results with regard to single parameter regressions. Dipolarity/polarisability and hydrogen... 

The electro-catalytic oxidation of methanol on a Ni-Cu alloy (NCA) with atomic ratio of 60/40 having previously undergone 50 potential sweep cycles in the range 0-600 mV vs. (Ag/AgCl) in 1 m NaOH was studied by cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (EIS). The electro-oxidation was observed as large anodic peaks both in the anodic and early stages of the cathodic direction of potential sweep around 420 mV vs. (Ag/AgCl). The electro-catalytic surface was at least an order of magnitude superior to a pure nickel electrode for methanol oxidation. The diffusion coefficient and apparent rate constant of methanol oxidation were found to be 2.16 × 10-4 cm2 s-1 and... 

A multiscale FD-KMC model has been developed to simulate the cyclic voltammetry test of a copper electrode in simple copper sulfate bath. In this coupled model, the FD code provides the cupric ion concentration on OHP for KMC code, while the KMC code provides the electrochemical properties of the copper electrode (surface activity and rate constants of redox reactions) as an input data for FD code. The changes in the electrode properties due to the atomistic phenomena (deposition dissolution and surface diffusion) have been studied for the present potentiodynamic system. The results showed that the CV process consists of some distinct stages, so that the electrode exhibits a specific... 

A novel method is used to link a 2D kinetic Monte Carlo code to a 1D finite difference code to construct a more realistic and efficient tool for simulating various electrochemical processes. This multiscale model is able to simulate the long-scale mass transfer of electroactive species in bath along with electrode surface phenomena at atomic scale simultaneously. An embedded atom method (EAM) has been used to evaluate the barrier energies of diffusion and redox reactions on electrode surface. The FD code provides the ion concentration on OHP for KMC code, while the KMC code provides the surface activity and rate constants of redox reactions as an input data for FD code. The electrochemical... 

A novel ɑ-NiMoO4/ɑ-MoO3 binary nanocomposite was fabricated by using facile method. The fabricated nanocomposite was characterized by various techniques, and the photocatalytic activity was evaluated in degradation of Acid blue 92 dye. Among of as-made photocatalysts with various weight ratios of ɑ-MoO3, ɑ-NiMoO4/ɑ-MoO3 (1:5%w/w) exhibited the best photocatalytic performance, and selected as optimum photocatalyst. Under optimum reaction conditions ([dye] = 10 mg L−1, [catalyst] = 200 mg L−1, and pH = 7.0), complete removal efficiency was obtained within 100 min. Also, the first-order rate constant value of reaction in the presence of ɑ-NiMoO4/ɑ-MoO3 was calculated to be 0.032 min−1 that was... 

Mud filtration happens during an overbalanced drilling operation that causes mud invasion into pores and fractures. The productivity of a formation is significantly affected by the invasion of the mud into the near-wellbore area during the mud loss process. A considerable number of studies have evaluated mud filtration statically; however, a few studies have considered the dynamic behavior of a mud loss process during overbalanced drilling, which results in the inadequate prediction of the mud loss volume and inflicted damage to the formation. In this study, a near-wellbore simulation system (NeWSS) was designed to evaluate the dynamic mud loss behavior using dimensionless parameters and... 

The simultaneous oxidation performance of benzene, toluene, ethylbenzene, and xylene (BTEX) by nanoscale calcium peroxide particles (nCaO2) activated with ferric ions (Fe(III)) and the mechanism of the enhancement of BTEX degradation by L-cysteine (L-cys) were investigated. The batch experimental results showed that the nCaO2/Fe(III)/L-cys process was effective in the destruction of BTEX in both ultrapure water and actual groundwater. A proper amount of L-cys could enhance BTEX degradation due to the promotion of Fe(II)/Fe(III) redox cycles by the participation of L-cys, but an excessive presence of L-cys would cause inhibition. Adding 1.0 mM L-cys to the nCaO2/Fe(III) system, the... 

This study demonstrated the prolonged benefits of polyvinyl-coated calcium peroxide (PVA@CP) in Fe(II)/nFeS mediated Fenton-like reaction. PVA@CP was prepared by a coating of PVA on calcium peroxide (CP) and synthesized nano-sized iron sulfide (nFeS) was characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) with energy dispersive spectroscopy (EDS) elemental mapping, X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES) and Fourier transmission infrared (FTIR) techniques. Trichloroethylene (TCE) degradation in various oxic environments (H2O2, CP, or... 

This study demonstrated the prolonged benefits of polyvinyl-coated calcium peroxide (PVA@CP) in Fe(II)/nFeS mediated Fenton-like reaction. PVA@CP was prepared by a coating of PVA on calcium peroxide (CP) and synthesized nano-sized iron sulfide (nFeS) was characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) with energy dispersive spectroscopy (EDS) elemental mapping, X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES) and Fourier transmission infrared (FTIR) techniques. Trichloroethylene (TCE) degradation in various oxic environments (H2O2, CP, or... 

Catalysts as the dynamo of chemical reactions along with solvents play paramount roles in organic transformations in long-lasting modes. Thus, developing effective and biobased catalysts in nontoxic solvents is highly in demand. In this report, carbon quantum dots (CQDs) functionalized with-lysine (Lys-CQDs) were generated from entirely nature-derived materials; they were demonstrated to be a promising catalyst for C-N bond formation in choline chloride urea (ChCl/U), a natural deep eutectic solvent (NADES). Among a number of synthesized CQDs, Lys-CQD turned out to be a powerful catalyst in the model reaction with aniline to afford phenyl urea. This type of transformation is important... 

The hydrogen abstraction reaction of the OH radical with CH 3CHF2 (HFC152-a) has been studied theoretically over a wide temperature range, 200-3000 K. Two different reactive sites of the molecule, CH3 and CHF2 groups have been investigated precisely, and results confirm that CHF2 position of the molecule is a highly reactive site. In this study, three recently developed hybrid density functional theories, namely, MPWB1K, MPW1B95, and MPW1K, are used. The MPWB1K/6-31+G(d,p) method gives the best result for kinetic calculations, including barrier heights, reaction path information and geometry of transition state structures and other stationary points. To refine the barrier height of each... 

The second-order rate coefficients for aromatic nucleophilic substitution reaction between 1-chloro-2,4-dinitrobenzene and aniline have been measured in aqueous solutions of ethanol and methanol at 25°C. The plots of rate constants versus mole fraction of water show a maximum in all-aqueous solutions. The effect of four empirical solvent parameters including hydrogen bond donor acidity (α), dipolarity/polarizability (π*). normalized polarity (ETN), and solvophobicity (Sp) has been investigated. This investigation has been carried out by means of simple and multiple regression models A dual-parameter equation of log k2 versus Sp and α was obtained in all-aqueous solutions (n = 41, r = 0.962,... 

The decomposition of methyl iodide on Cu(110) surface gives rise to the production of methane, ethane, and ethene over a wide range of its surface coverage. In this work a reaction mechanism based on the adsorption and subsequent surface dissociation(s) of methyl iodide followed by the recombination and desorption of the surface entities are proposed on the basis of the energetic criteria provided by the unity bond index-quadratic exponential potential method. To further amplify the arguments using the calculated activation energies of the surface reactions, desorptions, etc., the Arrhenius factor is obtained by simulation of the temperature-programmed desorption patterns fitted to the... 

Developing an efficient visible-light-driven photocatalyst is believed to be a practical solution for clean energy and environmental remediation. The present study aimed to broaden current knowledge of the graphitic carbon nitride (g-C3N4)-based plasmonic photocatalysts by decorating polydopamine-grafted g-C3N4 (PDA/g-C3N4) with silver nanoparticles (AgNPs). The nanocomposite was prepared using a facile synthesis method, while XPS and microscopy measurements confirmed the homogenous dispersion of AgNPs on PDA/g-C3N4. AgNPs successfully reduced the recombination rate of photoinduced electron-hole pairs. The calculated bandgap energy was decreased from 2.7 eV for pure g-C3N4 to 2.1 eV for... 

In the present study, the ACF-TiO2 catalyst was synthesised and used as a catalyst for the destruction of toxic cyanide in both synthetic and real industrial wastewaters. The ACF-TiO2 catalyst was found to be micro-porous with the BET surface area of 163 m2/g. The effect of different operational parameters such as catalyst concentration, cyanide concentration, operation time, and ozone concentration were target parameters in the present study. The findings show that 500 mg/L of catalyst is the optimum value for the photocatalytical process to completely oxidise 25 mg/L of cyanide within 10 min. While it was found that 300 mg/L of catalyst in the presence of 200 mg/h ozone is enough to remove...