Sharif Digital Repository

The radical chlorination of polyethylene was carried out in perchloroethylene solvent using chlorine gas and ultraviolet photoradiation to investigate a reaction kinetics model. The recurrent structure of chloromethylene (-CHCl-) and methylene (-CH 2 -) groups and the percentage of substituted chlorine were determined using hydrogen-nuclear magnetic resonance (H-NMR) (500 MHz) spectra. A kinetics model has been proposed for this reaction in which the conversion of methylene (-CH 2 -) units to chloromethylene (-CHCl-) units was considered to be the main reaction step. The simplified version of the obtained kinetics model indicates that the reaction is first order with respect to the chlorine... 

N,N′,N″-triethylenethiophosphoramide (Thiotepa) and its oxo analogue (Tepa) as the major metabolite are trifunctional alkylating agents with a broad spectrum of antitumor activity. In vivo and vitro studies show alkylation of DNA by Thiotepa and Tepa can follow two pathways, but it remains unclear which pathway represents the precise mechanism of action. In pathway 1, these agents are capable of forming cross-links with DNA molecules via two different mechanisms. In the first mechanism, the ring opening reaction is initiated by protonating the aziridine, which then becomes the primary target of nucleophilic attack by the N7-Guanine. The second one is a direct nucleophilic ring opening of... 

Thermodynamic and kinetic studies have been carried out on the adsorption of uranium(VI) by Amberlite IRA-910 resin. The adsorption process has been investigated as a function of adsorbate concentration, solution acidity, contact time, adsorbent dosage, and temperature. The experiments were preformed in batch mode, where uranium initial concentration on the solution samples were 185.5, 277.6 and 456.8 (mg/lit), sulfuric acid concentration range was 0.02-9 (mol/lit) and sorbent dosages were 0.2, 0.3 and 0.5 g. Equilibrium isotherm data were analyzed using Freundlich and Dubinin-Radushkevich isotherm models. The results showed that the adsorption process was well described by Freundlich... 

TiO2 nanorods have been successfully grown into a track-etched polycarbonate (PC) membrane by a particulate sol-electrophoretic deposition from an aqueous medium. The prepared sols had a narrow particle size distribution around 17 nm and excellent stability against aging, with zeta potentials in the range of 47-50 mV at pH 2. It was found that TiO2 nanorods were grown from dilute aqueous sol with a low, 0.1-M concentration. Fourier transform infrared spectroscopy (FT-IR) analysis confirmed that a full conversion of titanium isopropoxide was obtained by hydrolysis, resulting in the formation of TiO2 particles. X-ray diffraction (XRD) results revealed that TiO2 nanorods dried at 100 °C were a... 

The electrodeposition of nickel was studied using electrochemical techniques in different electrolytes and various agents. The voltammetry analysis clearly showed that the electrodeposition of nickel was a diffusion-controlled process associated with a typical nucleation process. The current transients represented instantaneous nucleation with a typical three-dimensional (3D) growth mechanism. Scharifker's equations were derived for instantaneous and progressive nucleation of the 3D growth of the spherical centers under diffusion-controlled condition. The number of nucleation sites increased with the increment in overpotential and Ni 2+ concentration. Atomic force microscopy was used to... 

ABSTRACT: Pyrolysis, so-called devolatilization, is one of the first steps of all thermochemical processes occurring in an inert atmosphere. The authors discuss the main kinetic features of heavy oil pyrolysis, on the basis of the data derived m from a TGA analysis and by using a kinetic model. The samples were heated over a range of temperature from 400 K to 430°C at various heating rates between 10 and 80°C/min. Experimental results showed that the effect of time is considerable in the case of tar conversion, compared to char and gases  

Biodiesel is considered an alternative replacement for petroleum diesel, and enzymatic reaction is one method for biodiesel production. Understanding the kinetics of this reaction is important to achieve higher production rates. The kinetics of transesterification of castor oil using Novozym 435 was investigated in this study. The genetic algorithm was employed for estimation of kinetic parameters including Vmax, KmTG, and KmA in the Ping Pong kinetic model at different temperatures. In most enzymatic reactions that follow the Ping Pong mechanism, inhibition by alcohol has been taken into consideration. Here, we examined a competitive inhibition mechanism and found no inhibition effect at... 

We synthesize TiO2@SnO2 core-shell nanoparticles (NPs) by a facile two-step aqueous sol-gel method and their photocatalytic activity is compared with the pure TiO2 and SnO2 NPs for degradation of methylene blue under UV irradiation. The chemical property, crystal structure and morphology of the synthesized samples are studied by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Field emission scanning electron microscopy (FE-SEM) and transmission electron microscope (TEM) techniques. The mechanisms of electron–hole recombination and separation of charge carriers are studied by photoluminescence (PL) and diffuse reflectance spectroscopy (DRS). Furthermore, the kinetics... 

In this research, a solid 1%Li/Ca-La mixed oxide catalyst was prepared using co-precipitation method followed by wet impregnation. The prepared catalyst was used in the transesterification reaction of canola oil and methanol for biodiesel synthesis. The effects of calcination and reaction temperatures were investigated on the activity of the catalyst. In addition, rate of the reaction was studied through a kinetic model for which parameters were determined. Surface properties and structure of the catalyst were characterized through the powder X-ray diffraction (XRD), thermogravimetry/derivative thermogravimetry (TG/DTG), and Fourier transform infrared spectroscopy analysis. All these... 

In this work, the potential for the auto-ignition of Iranian heavy oil during in situ combustion (ISC) process conditions was studied. Kinetic studies were carried out using thermal analysis techniques. Effects of oxygen partial pressure, reservoir pressure, and clay on the auto-ignition condition were investigated. Based on the experimental results obtained, a kinetic equation was derived for each of the different oil samples in the presence of different sands. The effect of partial pressure of oxygen in the injected air showed that at atmospheric pressure, low temperature combustion (LTC) was initiated at 275°C. Also, enriching the injected air by oxygen lowers the initial LTC temperature... 

The steam reforming of ethylene glycol, a simple model compound for biomass-derived liquids, is considered to be an environmentally green process for producing renewable hydrogen. Both Pt and Ni species are known for their catalytic activity under steam reforming reaction conditions. In this investigation, alumina supported Ni-Pt bimetallic catalysts (X wt% Ni-Y wt% Pt/Al2O3 named XNi-YPt) were employed for steam reforming of ethylene glycol. The prepared catalysts were characterized by XRD, BET, H2-TPR, H₂-Chemisorption, and TEM. It was observed that Ni/Pt ratio strongly affected the redox behavior, BET surface area, and particle size of the samples that in turn affected their catalytic... 

A gas-phase heterogeneous kinetics is described over perovskite with formula La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF) for the oxidative coupling of methane under differential conversion conditions in a microcatalytic fixed-bed reactor. The ethane (C2H6) and carbon oxides (COX) formation and methane conversion rates were obtained as a function of methane and oxygen partial pressure under experimental conditions of: 0.20 < PC H4 < 0.82 atm, 0.04 < PO2 < 0.15 atm, and 1073 < T < 1173 K. The different kinetic models were examined and two Eley-Rideal mechanisms (a and b) were successfully performed to fit the experimental data into the theoretical relations from which two mechanisms having a first step of... 

We have studied the stochastic parameters of surface iron oxide nanograin chains, 97 nm in diameter and 2.4 νm in length, prepared at different annealing temperatures, using atomic force microscopy (AFM) spectral analysis. In this regard, the roughness of the thin films including self-assembled twisted nanograin chains has been analysed and characterized using the height-height correlation function, the roughness exponent as well as the power spectrum density of the AFM profiles and their gradient, for the different annealing temperatures. The tip convolution effect on the stochastic parameters under study has also been investigated. The kinetics of the formation of nanograins on the film... 

In this study, H4Ti5O12 nanotubes have been prepared as Li+ adsorbent by acid treatment of Li4Ti5O12 nanotubes. Li4Ti5O12 nanotubes were synthesized via a hydrothermal method in which TiO2(B) nanNotubes were used as a precursor. The prepared Li-ion sieve showed a significant high ion-exchange capacity (160.6 mgg-1) for lithium ions due to its large specific surface area of 115.4 m2 g-1 compared to the other related studies. The kinetics and isotherm investigation revealed that the pseudo-second-order equation well described the adsorption kinetics, and the Langmuir model well fitted the isotherm data. Furthermore, the low value of adsorption energy obtained from the Dubinin-Radushkevitch... 

In this research work, the pressure leaching of chalcopyrite concentrate with oxygen was studied. Experiments were carried out under conditions of the solid–liquid ratio of 0.1, agitation speed of 750 rpm, and sulfuric acid concentration of 2 M in a stainless-steel autoclave system under 0.6 to 1 MPa oxygen gas. Central composite design was used to design experiments, and three factors of temperature, time, and oxygen pressure were selected as the design variables. A linear model for %Cu and a quadratic model for %Fe were proposed by Minitab Software. The results showed that temperature is the most effective factor in chalcopyrite leaching. Under optimal conditions, 93.08% of copper with the... 

The second-order rate constants for cycloaddition reaction of cyclopentadiene with naphthoquinone were determined spectrophotometrically in various compositions of 1-(1-butyl)-3-methylimidazolium terafluoroborate ([bmim]BF4) with water and methanol at 25°C. Rate constants of the reaction in pure solvents are in the order of water > [bmim]BF 4 > methanol. Rate constants of the reaction decrease sharply with mole fraction of the ionic liquid in aqueous solutions and increase slightly to a maximum in alcoholic mixtures. Multi-parameter correlation of logk 2 versus solute-solvent interaction parameters demonstrated that solvophobicity parameter (Sp), hydrogen-bond donor acidity (α) and... 

The purpose of this study is to investigate production of high quality ammonium uranyl carbonate (AUC) from “uranyl nitrate + ammonium bicarbonate”, or “uranyl nitrate + sodium carbonate” precursor solutions, by controlled injection of ammonium carbonate solution which could be applicable in material testing reactor (MTR) fuel production plant for recycling of rejected uranium oxide powder. The experimental observations revealed: at pHs higher than 6, precipitation proceeds with formation of no intermediate, thus ensuing a better morphology and size distribution of the AUC products. The results of scanning electron microscopy, X-ray diffraction, particle size analysis, and uranium content... 

Low accuracy, requirement of expensive instruments, derivatization and multi-step sample preparation, inconsistencies during the fabrication process, time-consuming procedures and utilization of eco-unfriendly chemicals are some limitations of various developed methods for detection of 4-methylimidazol (4-MeI). Herein, a rapid and miniaturized fluorescent probe based on the ultrasound‒assisted formation of carbon dots (CDs) in a metallic deep eutectic solvent (MDES) was developed and conveniently implemented to detect 4-MeI in commercial dark soft drinks. In-situ synthesis of CDs-chelated metals in the presence of the target analyte facilitates a kinetically fluorescence emission with no... 

In this research, a green solid catalyst of phosphomolybdic acid (HPA) prated on Chitosan was synthesized to produce biodiesel. The prepared catalyst was characterized using Fourier Transform Infrared spectroscopy (FTIR), Field Emission Scanning Electron Microscope (FESEM), Energy Dispersive X-Ray (EDX), X-ray diffraction (XRD), and XRF analyses. The catalyst was applied in microwave-assisted trans-esterification of Pomegranate oil, and the biodiesel production process was optimized by response surface methodology based on central composite design (RSM-CCD). The effect of influential reaction parameters, including time (33–142 min), catalyst weight (0.15–5.6 wt%), and methanol to oil molar...