Sharif Digital Repository

A theoretical study of the kinetics and mechanism of the cyclization of citronellal in the gas phase was performed using density functional theory methods at the B3LYP level of theory with 6-311G, 6-311G*, 6-31G**, 6-311G**, 6-311 þ G and 6-311 þ þ G basis sets at 298.15 K, 433.15 K, and 473.15 K. Equilibrium molecular geometries and harmonic vibrational frequencies of the reactant, transition state and products were calculated. Rate constants and activation thermodynamic parameters were calculated and showed a fairly good agreement with experimental results. The effect of solvent polarity on the reaction was studied. These calculations indicated that the reaction proceeds through an... 

The functionalized copper oxide–zinc oxide nanocomposite (FCZN) was synthesized and characterized using Fourier transform infrared, scanning electron microscopy, X-ray diffraction, X-ray fluorescence, and BET. Dye removal from aqueous solution was done in a batch system using FCZN as an adsorbent. The effects of adsorbent dosage, initial dye concentration, pH, temperature, and additive salts on dye removal were investigated. Isotherms, kinetics, and thermodynamics of dye adsorption were studied. Equilibrium and kinetic data were fitted by Langmuir isotherm and pseudo-second-order kinetic, respectively. The thermodynamic data showed that dye adsorption was spontaneous, endothermic, and... 

An investigation of the kinetic and mechanism of CO hydrogenation reaction was performed on impregnated Co-Ni/Al2O3. Determination of kinetic parameters from the experiments was carried out in a micro fixed-bed reactor. Kinetic evaluations were performed under various operational conditions of T = 473–673 K, p = 1–14 bar, H2/CO = 1–3, and GHSV = 4,500 hr−1. Kinetic models and rate equations for CO consumption were obtained by using two main-type rate equations of Langmuir-Hinshelwood-Hougen-Watson (LHHW) and Eley-Rideal (ER). Estimation of various kinetic parameters was performed using a nonlinear regression method. According to the obtained experimental results and using statistical... 

The prediction of interfacial turbulence characteristics is one of the still challenging of two-phase stratified flow. The evaluation of some important parameters such as interfacial heat transfer coefficient based on turbulence kinetic energy and turbulence dissipation rate in some models, intensifies the importance of turbulence flow correct simulation. High gradient of velocity and turbulence kinetic energy at the interface of two-phase stratified flow leads to a major overestimation or underestimation of flow characteristics without any special treatment. Consideration of a source function of turbulence eddy frequency at the interface is one of the common solution employed in past... 

Cylindrical hydrogels have a wide variety of applications in microfluidics; for example, they serve as micro-valves, micro-mixers, and micro-lenses. The main advantages of them can be mentioned as their autonomous functionality due to their responses to environmental stimuli and simple geometry. Furthermore, functionally graded hydrogels have recently found applications in hydrogel actuators. Therefore, in this work, the kinetics of swelling, shrinking, and force generation of cylindrical functionally graded temperature-responsive hydrogels are investigated. Kinetics of cylindrical structure is investigated analytically by developing a mathematical model based on available constitutive... 

In this work, the potential of auto-ignition of heavy oil during in-situ combustion (ISC) process was studied. Kinetic studies were carried out using Thermo Gravimetric Analyzer (TGA), Differential Scanning Calorimetry (DSC) and Accelerating Rate Calorimetric (ARC) techniques. Effects of oxygen partial pressure, reservoir pressure and clay on auto ignition condition were investigated on a number of different heavy oil samples from south west Iran mixed with silica sand or crushed carbonate rock and clay. Based on the experimental results obtained by TGA runs, the kinetic equation was derived for different oil samples in the presence of different sands. Effect of partial pressure of oxygen in... 

For large and complex reacting systems, computational efficiency becomes a critical issue in process simulation, optimization and model-based control. Mechanism simplification is often a necessity to improve computational speed. We present a novel approach to simplification of reaction networks that formulates the model reduction problem as an optimization problem and solves it using genetic algorithm (GA).The aim of simplification kinetics modeling is to derive the simplest reaction system, which retains the essential features of the full system. Numerical results for H2/O2 combustion reaction mechanism illustrate the potential and proficiency of this approach  

Background: Dynamic knee valgus (DKV) is a common lower extremity movement disorder among females. This study aimed to investigate kinematic couplings between lower extremity joints in female junior athletes with DKV during single and double-leg landing and gait. Methods: Twenty-six physically active female junior athletes (10–14 years old) with DKV were recruited. Kinematic couplings between rearfoot, tibia, knee, and hip were extracted using eight Vicon motion capture cameras and two force plates. Zero-lag cross-correlation coefficient and vector coding were used to calculate kinematic couplings between joints during physical tasks. Paired t-test and Wilcoxon tests were run to find... 

The current study presents a simple and scalable method for the synthesis of (aminomethyl)phosphonic acid-functionalized graphene oxide (AMPA-GO) adsorbent. The chemical structure of the new material was disclosed by different instrumental analyses (e.g. FTIR, Raman, XPS, AFM, TEM, XRD, CHN, and UV), and two pertinent mechanisms namely nucleophilic substitution and condensation were suggested for its formation. Adsorption experiments revealed that both AMPA-GO and plain GO have a high affinity toward Th(IV) ions, but the AMPA-GO is superior in terms of adsorption capacity, rate of adsorption, selectivity, pH effect, etc. Indeed, the AMPA-GO can uptake Th(IV) nearly instantaneously, and... 

Manual material handling (MMH) tasks were evaluated and compared under different lifting conditions. For the theoretical evaluations, a two-dimensional sagittally symmetric human-body model was established to compute the moment and joint load time histories for MMH tasks for a variety of different lift specifications and constraints such as lifting durations, loads, and modes. Nonlinear control techniques and genetic algorithms were utilized in the optimizations to explore optimal lifting patterns. Since the kinetic measures such as joint moments are vital metrics in the assessment of the likelihood of injury, the simulation results obtained may be compared using these metrics for each lift... 

This study is focused on the development of a systematic computational approach which implements Genetic Algorithm (GA) to find the optimal rigorous kinetic models. A general Kinetic model for hydrogenolysis of dibenzothiophene (DBT) based on Langmuir Hinshelwood type has been obtained from open literature. This model consists of eight continuous parameters(e.g., Arrhenus and Van't Hoff parameters) and six discrete parameters representing the order of the reaction with respect to each concentration. The optimal value of these parameters have been obtained based on Genetic Algorithm. Furthermore, the best type of Genetic operators and their corresponding parameters for this type of problems... 

Chitin was extracted from shrimp shells and then deacetylated to obtain chitosan. The degree of deacetylation of the chitosan was determined to be 0.76 using pH-metric titration. A large number of cyanide functional groups were introduced onto chitosan by grafting with polyacrylonitrile as an efficient way of modification. The graft copolymerization reactions were carried out under argon atmosphere in a homogeneous aqueous phase (containing a small portion of acetic acid) by using eerie ammonium nitrate as an initiator. Evidence of grafting was obtained by comparing FTIR spectra of chitosan and the graft copolymer as well as solubility characteristics of the products. The synthetic... 

In this research the characteristics of free (partially purified) and immobilized (mould pellets of Absidia griseola) α-galactosidase have been investigated. Inhibition studies of the enzyme showed that p-nitrophenol and sucrose do not have any inhibitory effect on the enzyme, but that galactose is a competitive inhibitor. In the immobilized form, inhibition was lower than in the free enzyme and the level of inhibition decreased as the temperature increased. The activity and stability of free and immobilized enzyme were investigated with respect to temperature, and the results showed that the optimal temperature range of the free enzyme was 45-50°C, while the immobilized enzyme had an... 

The deactivation of solid acid catalysts in liquid-phase alkylation of isobutane with butenes was investigated. The role of pore mouth plugging, in particular, was studied and it was found that it had a significant effect on the deactivation behavior. Simple explicit correlations were developed for catalyst lifetime in a CSTR, both in terms of time-on-stream and butene turnover per catalyst weight. The correlations were tested using available experimental data from the literature and a reasonable agreement was observed. It was shown that for a zeolitic catalyst the butene turnover per catalyst weight was proportional to the square root of catalyst loading, while it was inversely proportional... 

The effect of the nucleating agent masterbatch carrier resin on the nonisothermal crystallization of a pipe-grade polypropylene block copolymer was investigated at three different cooling rates using differential scanning calorimetry (DSC). Bis(3,4-dimethylibenzylidene) sorbitol (DMDBS), a well-known, third-generation sorbitol derivative, was used as a nucleating agent in this study. Crystallization kinetic parameters obtained from DSC cooling curves showed that incorporation of a nucleating agent by means of a masterbatch increased the crystallization rate by approximately two times compared to that of the sample with the same concentration of nucleating agent without the use of a... 

The current study presents a simple and scalable method for the synthesis of (aminomethyl)phosphonic acid-functionalized graphene oxide (AMPA-GO) adsorbent. The chemical structure of the new material was disclosed by different instrumental analyses (e.g. FTIR, Raman, XPS, AFM, TEM, XRD, CHN, and UV), and two pertinent mechanisms namely nucleophilic substitution and condensation were suggested for its formation. Adsorption experiments revealed that both AMPA-GO and plain GO have a high affinity toward Th(IV) ions, but the AMPA-GO is superior in terms of adsorption capacity, rate of adsorption, selectivity, pH effect, etc. Indeed, the AMPA-GO can uptake Th(IV) nearly instantaneously, and... 

The leaching kinetics of stibnite in basic solution has been investigated. Spherical pellets of antimony sulphide were dissolved in 1 molar sodium hydroxide solutions at different temperatures. It was found that the shrinking core with ash layer model could satisfactorily explain the dissolution process. Using this model, it was found that initially the rate controlling step was a chemical reaction with activation energy of 10.2 kJ/mol. As the ash layer built up, diffusion through the ash layer became the rate controlling step. The activation energy for this step was found to be 33.4 kJ/mol. It was also observed that smaller particle size, larger solid to liquid ratio, and higher NaOH... 

Due to great commercial application of protease, it is necessary to study kinetic characterization of this enzyme in order to improve design of enzymatic reactors. In this study, mathematical modeling of protease enzyme production kinetics which is derived from Bacillus licheniformis BBRC 100053 was studied (at 37°C, pH 10 after 73 h in stationary phase, and 150 rpm). The aim of the present paper was to determine the best kinetic model and kinetic parameters for production of protease and calculating K i (inhibition constant) of different inhibitors to find the most effective one. The kinetic parameters K m (Michaelis-Menten constant) and V m (maximum rate) were calculated 0.626 mM and... 

The adsorption of nickel ions in an aqueous solution system was measured using zeolitic imidazolate framework-8 (ZIF-8) nanoadsorbent. ZIF-8 crystals were synthesized using the hydrothermal method. Nanoadsorbent was characterized by FTIR, XRD, SEM and N2 adsorption analysis. ZIF-8 crystals showed a high surface area of 1303 m2/g and particle size 100–150 nm. The Langmuir and Freundlich isotherms model were used to analyze the data. The sufficiently high R2 value of 0.996 resulted from the Langmuir isotherm model demonstrated the perfect performance of this model. The kinetic data were analyzed using the pseudo-first-order and pseudo-second-order models of types 1–4. Kinetic studies of the... 

A kinetic model for growth of ZnO nanorods via vapor-liquid-solid (VLS) mechanism based on the bulk diffusion of Zn atoms through the Au-Zn droplet is presented. The dependences of the growth rate on size are given quantitatively. A general expression for the growth rate of nanorods during VLS process is derived. The derived formula shows the dependences of growth rate on lateral size of nanorods, concentration and supersaturation of Zn atoms in the liquid droplet. Based on the presented kinetic model the smaller nanorods have faster growth rate. Au-catalyzed ZnO nanorods are grown by chemical vapor transport and condensation (CVTC) process experimentally. Theoretical and experimental...