Sharif Digital Repository

Rate constants, k A, for the aromatic nucleophilic substitution reaction of 2-chloro-3,5-dinitropyridine with aniline were determined in different compositions of 2-propanol mixed with hexane, benzene, and 2-methylpropan-2-ol and 1-ethyl-3-methylimidazolium ethylsulfate ([Emim][EtSO4]) with dimethyl sulfoxide at 25°C. The obtained rate constants of the reaction in pure solvents are in the following order: 2-methylpropan-2-ol > dimethyl sulfoxide > 2-propanol > hexane > benzene > [Emim][EtSO4]. Molecularmicroscopic solvent parameters corresponding to the selected binary mixtures were utilized to study the kinetics of a nucleophilic substitution reaction in order to investigate and compare the... 

The conductive CuCo2O4 spinel coating is applied on the surface of the AISI 430 ferritic stainless steel by the dip-coating sol-gel process and it is evaluated in terms of the microstructure, oxidation resistance and electrical conductivity. The results show that the CuCO2O 4 coating forms a double-layer scale consisting of a Cr, Fe-rich subscale and Cu-Co spinel top layer after 500 h in air at 800 °C. This scale is protective, acts as an effective barrier against Cr migration into the outer oxide layer and alleviates the cathode Cr-poisoning. The oxidation resistance is significantly enhanced by the protective coating with a parabolic rate constant of 5.8 × 10-13 gr2 cm-4 s -1, meanwhile... 

In this research the application of design of experiment (DOE) coupled with the artificial neural networks (ANN) in kinetic study of oxidative dehydrogenation of propane (ODHP) over a vanadium-graphene catalyst at 400-500 °C and a method of data collection/fitting for the experiments were presented. The proposed reaction network composed of consecutive and simultaneous reactions with kinetics expressed by simple power law equations involving a total of 20 unknown parameters (10 reaction orders and 5 rate constants each expressed in terms of a pre-exponential factors and activation energies) determined through non-linear regression analysis. Because of the complex nature of the system, neural... 

TiO2 nanoparticles were synthesized by hydrothermal assisted sol-gel technique. The preparation parameters including pH value, the amount of water, titanium tetra isopropoxide content, temperature and time of hydrothermal process were investigated by Taguchi statistical experiments to determine the influence of synthesizing variables on the optimal conditions and to realize the highest degree of crystallinity or smallest crystallite size. X-ray diffraction (XRD) analysis and direct band gap energy (Eg) values, measured via diffuse reflectance spectra (DRS), proved that all the samples consist of anatase as a unique phase. Transmission electron microscopy (TEM) and specific surface area... 

Rate constants, k A, for the aromatic nucleophilic substitution reaction of 2-chloro-3,5-dinitropyridine with aniline were determined in different compositions of 2-propanol mixed with hexane, benzene, and 2-methylpropan-2-ol and 1-ethyl-3-methylimidazolium ethylsulfate ([Emim][EtSO4]) with dimethyl sulfoxide at 25 C. The obtained rate constants of the reaction in pure solvents are in the following order: 2-methylpropan-2-ol > dimethyl sulfoxide > 2-propanol > hexane > benzene > [Emim][EtSO4]. Molecularmicroscopic solvent parameters corresponding to the selected binary mixtures were utilized to study the kinetics of a nucleophilic substitution reaction in order to investigate and compare the... 

In an attempt to reduce the oxidation and Cr evaporation rates, various protective coating layers with a nominal composition of NiCo 2-xFexO4 (x = 0, 0.5, 1) were deposited on the SUS 430 ferritic stainless steel substrate, as interconnect for solid oxide fuel cell application, by sol-gel dip coating method. Then, the coated samples were soaked at 750 C for 2.5 h in N2 and subsequently for 2.5 h in air. Phase composition and microstructure of the coatings were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Moreover, long-term isothermal oxidation experiment and area specific resistance (ASR) measurement were also carried out on the coated samples. Results... 

The microscopic features of binary solvent systems formed by molecular solvents (methanol, ethanol, 2-methylpropan-2-ol, water, pyridine, acetonitrile, 1-propanol, 2-propanol, dimethylformamide) and the ionic liquid ([bmim]BF 4) as cosolvent were used to select mixed solvents with particular characteristics. Molecular-microscopic solvent parameters corresponding to these binary mixtures were utilised to study the kinetics of the nucleophilic substitution reaction between 2-chloro-3,5-dinitropyridine and aniline to investigate and compare the effects of the solvents on a model chemical reaction. For these mixtures, the solvation behaviour is dominated by both the dipolarity/ polarisability... 

We have studied systematically photocatalytic properties of the vertically aligned ZnO@CdS core-shell nanorods where the features were grown through a multistep procedure including sol-gel for the formation of ZnO seed layer, hydrothermal process to grow ZnO nanorods, and successive ion layer adsorption and reaction (SILAR) process to deposit CdS nanoshells onto the ZnO nanorods. Formation of the ZnO seed layer and vertically aligned ZnO nanorods (d ∼ 40 nm) with a hexagonal cross-section was confirmed by AFM and SEM imaging. Successful capping of ZnO nanorods with homogeneous CdS nanocrystallites (∼5 nm) was ascertained by HRTEM diffraction and imaging. Optical properties of the samples... 

Ship-in-a-bottle complex of nickel(II) containing the ligand N,N′-bis(2,4-dihydroxyacetophenone)-2,2-dimethylpropandiimine (H 2{salnptn(4-OH)2}) has been synthesized in zeolite Y. The characteristics of the encapsulated complex are identified by the methods of EDX, SEM, XRD, FT-IR and cyclic voltammetry. A catalytic effect in the electrochemical oxidation of glucose, fructose and sucrose, and a blocking effect in stevioside oxidation are demonstrated on the Ni II{salnptn(4-OH)2}-Y/CPE. The effects of some parameters, such as potential scan rate and concentration of carbohydrates are investigated. The rate constants for the catalytic reaction (k′) of carbohydrates are also obtained. The... 

By combination of 1-ethyl-3-methyl immidazolium ethyl sulfate as a typical room temperature ionic liquid (IL) and graphene oxide (GO) nanosheets, a nanocomposite was introduced for improving the direct electrochemistry and electrocatalytic activity of glucose oxidase (GOx). The enzyme on the IL-GO-modified glassy carbon electrode exhibited a quasireversible cyclic voltammogram corresponding to the flavine adenine dinucleotide/FADH2 redox prosthetic group of GOx. At the scan rate of 100 mV s-1, the enzyme showed a peak-to-peak potential separation of 82 mV and the formal potential of -463 mV (vs Ag/AgCl in 0.1 M phosphate buffer solution, pH 7.0). The kinetic parameters of the charge transfer... 

The FT reaction involves the conversion of syngas which is derived from natural gas or coal to different kinds of products according to the operating conditions and the type of the catalyst. In other words, it is a practical way to convert solid fuel (coal) and natural gas to various hydrocarbons (C1-C60) and oxygenates such as alkanes, alkenes etc. The main products of the reaction are naphtha and gasoline. This paper deals with developing a proper product distribution model for FT process using the appropriate kinetic model, optimizing the respective rate constants while applying them in product distribution equations. The results revealed only 8.09% deviations from the olefin experimental... 

Nickel-modified glassy carbon electrode (GC/Ni) prepared by galvanostatic deposition was used for the electrocatalytic oxidation of glucose in alkaline solutions where different electrochemical methods were employed. In cyclic voltammetry studies, in the presence of glucose an increase in the peak current of the oxidation of nickel hydroxide is followed by a decrease in the corresponding cathodic current. This suggests that the oxidation of glucose is being catalyzed through mediated electron transfer across the nickel hydroxide layer comprising nickel ions of various valence states. Under the chronoamperometric regime, the reaction followed a Cottrellian behavior and the diffusion... 

Nickel modified graphite electrodes (G/Ni) prepared by galvanostatic deposition were examined for their redox process and electrocatalytic activities towards the oxidation of methanol, ethanol, 1-propanol and 2-propanol in alkaline solutions. The methods of cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (EIS) were employed. In CV studies, the electrochemical response, peak current varied in the order of MeOH > EtOH > 1-PrOH > 2-PrOH. Under the CA regime, a higher catalytic rate constant obtained for methanol oxidation was in agreement with CV measurements. Lower charge transfer resistance was obtained for low carbon alcohols oxidation and significantly higher... 

Ni II-(N,N′-bis(2,4-dihydroxyacetophenone)-2, 2-dimethylpropandiimine (Ni II{salnptn(4-OH) 2}) complex has been encapsulated within the supercage of zeolite-NaY by reacting Ni 2+-exchanged NaY with the flexible Schiff-base ligand that diffuses into the cavities. The encapsulated complex is characterized by EDX, scanning electron microscopy, powder X-ray diffraction, FT-IR, and cyclic voltammetry studies. Density functional calculation is being carried out on both the free nickel Schiff-base complex and that encapsulated in NaY zeolite to investigate changes in structural parameters, energies of the HOMO and LUMO, and absolute hardness and softness. Electrochemical properties of the NaY... 

Horseradish peroxidase (HRP) was successfully immobilized on amine functionalized TiO 2-coated multiwalled carbon nanotubes (NH 2-TiO 2-CNTs) by a convenient and efficient method. Electrochemical impedance spectroscopy, cyclic voltammetry and amperometry were applied to characterize the HRP/NH 2-TiO 2-CNT nano-composite. These techniques showed that the NH 2-TiO 2-CNTs greatly enhance the electron transfer between HRP and the modified electrode. Owing to the redox reaction of the electroactive centre of HRP, the HRP/NH 2-TiO 2-CNTs modified electrode exhibited a pair of quasi-reversible peaks with a peak-to-peak separation (ΔE p) of 70.6mV and a formal potential (E 0′) of -367.65mV (versus... 

Dinuclear cis-dioxomolybdenum(VI) complex [{MoO 2(Bz 2Benzenediyldtc)} 2] coordinated by a quadradentate dithiocarbamate (Bz 2Benzenediyldtc 2- = 1,4-benzenediylbis(benzyldithiocarbamate)(2-)) has been prepared and characterized by elemental analysis, 13C NMR, IR and UV-vis spectroscopy. The kinetics of the oxygen atom transfer between [{MoO 2(Bz 2Benzenediyldtc)} 2] and PPh 3 was studied spectrophotometrically in CH 2Cl 2 medium at 520 nm and four different temperatures, 288, 293, 298 and 303 K, respectively. The reaction follows second order kinetics with the rate constant k = 0.163(2) M -1 S -1 and its increasingly strong absorption at 520 nm clearly indicate the formation of a μ-oxo... 

Electro-oxidation of methanol in alkaline solution at a glassy carbon electrode electrochemically modified by a conductive polymeric meso-tetra(4-carboxyphenyl)porphyrinato nickel(II), abbreviated as poly-NiTCPP and also meso-tetra(4-carboxyphenyl)porphyrin with incorporated nickel(II) cations, abbreviated as, poly-TCPP/Ni, were investigated and compared. Both films were prepared by oxidative electro-polymerization of complexes by repetitive cyclic voltammetry (RCV) in 0.1 M NaOH aqueous solution. The electrochemical properties and behaviors and also kinetic values of both films have been characterized and compared using cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical... 

Aromatic nucleophilic substitution reaction of 1-fluoro-2,4-dinitrobenzene with para-substituted and meta-substituted anilines was kinetically investigated in the mixtures of ethyl acetate and methanol at room temperature. The correlation of second-order rate coefficients with Hammett's substituent constants yields a fairly linear straight line with negative slope in different mole fractions of ethyl acetate-methanol mixtures. The measured rate coefficients of the reaction demonstrated a dramatic variation in ethyl acetate-methanol mixtures with the increasing mole fraction of ethyl acetate. Linear free energy relationship (LFER) investigations confirm that polarity has a major effect on the... 

Micro arc oxidation technique, as a facile and efficient process, was employed to grow sulfur doped titania porous layers. This research sheds light on the photocatalytic performance of the micro arc oxidized S-TiO2 nano-porous layers fabricated under pulse current. Morphological and topographical studies, performed by SEM and AFM techniques, revealed that increasing the frequency and/or decreasing the duty cycle resulted in formation of finer pores and smoother surfaces. XRD and XPS results showed that the layers consisted of anatase and rutile phases whose fraction was observed to change depending on the synthesis conditions. The highest anatase relative content was obtained at the... 

Since ultraviolet (UV) irradiation cannot be applied for a long time in practical applications, it is necessary to develop a narrow band gap photocatalyst to decompose environmental pollutants under visible irradiation. In this research, (WO3)x-(TiO2)1-x nano-porous layers were fabricated by micro arc oxidation (MAO) and influence of the electrical current type on their physical and chemical properties was investigated. Morphological studies, performed by SEM technique, revealed that pore size and roughness decreased with the frequency and increased with the duty cycle. The pulse-grown layers had a finer structure when compared to those fabricated under direct current. XRD and XPS results...