Sharif Digital Repository

The reaction kinetics of 2-bromo-5-nitro thiophene with piperidine was studied in a solvent with a mixture of propan-2-ol with methanol and n-hexane at 25°C. The measured rate coefficients of the reaction demonstrated dramatic variations in propan-2-ol–n-hexane mixtures and mild variations in propan-2-ol–methanol system. The second-order rate coefficients of the reaction, kA, decreased sharply with n-hexane content. The multiparameter correlation of log kA versus molecular-microscopic solvent parameters shows interesting results in these solutions. Linear free energy relationship investigations confirm that polarity has a major effect on the reaction rate and hydrogen bond ability of the... 

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... 

Solute-solvent and solvent-solvent interactions were investigated for binary mixtures of an ionic liquid (IL) 2-hydroxy ethylammonium formate as with methanol, ethylene glycol and glycerol. The physicochemical properties of the solvent mixtures at 25 °C, over the whole range of mole fractions, were determined using solvatochromic probes. High normal polarity ( ENT ) in the alcohol-rich region confirms solute-solvent interactions in this medium. Dipolarity/polarizability (π ∗) show a different trend to ENT with a positive deviation from ideal behavior in IL-glycerol mixtures. However, these deviations for other solvent mixtures are insignificant. Contrary to what is observed for ENT and π ∗,... 

Structural and intermolecular interactions of solvatochromic probes 4-nitroaniline, 4-nitroanisole, and Reichardt’s dye were investigated in the binary mixtures of 2-hydroxy ethylammonium formate as an ionic liquid with N,N-dimethyl formamide, dimethyl amine, and dimethyl sulfoxide. Solvatochromic parameters (ETN, normalized polarity parameter; π*, dipolarity/polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen -bond donor acidity) were determined in ionic liquid mixtures at 25 °C using UV−vis spectroscopy. ETN parameters obtained from absorbance of Reichardt’s dye within various mixtures of ionic liquid were observed to be higher than predicted values from ideal additive... 

Structural and molecular-microscopic properties of the solvatochromic probes 4-nitroaniline, 4-nitroanisole, and Reichardt’s dye were investigated in binary mixtures of ethylammonium propionate with methanol, ethanol, 1-propanol and 2-propanol. Solvatochromic parameters (α, hydrogen-bond donor acidity; β, hydrogen-bond acceptor basicity; π*, dipolarity/polarizability; ENT , normalized polarity parameter) in different binary mixtures of ionic liquid with molecular solvents were determined with UV–Vis spectroscopy. The ENT parameters show nearly ideal trends in all solvent mixtures, but the other parameters show different behavior in the mixtures. The π* parameters show a negative deviation... 

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 solvatochromic parameters (ETN, normalized polarity parameter; π*, dipolarity/polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen-bond donor acidity) were determined for binary solvent mixtures of 1-(1-butyl)-3-methylimidazolium tetrafluoroborate ([bmim]BF4) with water, methanol, and ethanol at 25°C over the whole range of mole fractions. In nonaqueous solutions, the ETN value of the mixture increases with mole the fraction of [bmim]BF4 and then decreases gradually to the value of pure [bmim]BF4. Positive deviation from ideal behavior was observed for the solvent parameters ETN, π*, and α, whereas the deviation of the β parameter is negative. The applicability of the combined... 

The reaction kinetics of 2-bromo-5-nitro thiophene with piperidine was studied in a solvent with a mixture of propan-2-ol with methanol and n-hexane at 25°C. The measured rate coefficients of the reaction demonstrated dramatic variations in propan-2-ol-n-hexane mixtures and mild variations in propan-2-ol-methanol system. The second-order rate coefficients of the reaction, kA, decreased sharply with n-hexane content. The multiparameter correlation of log kA versus molecular-microscopic solvent parameters shows interesting results in these solutions. Linear free energy relationship investigations confirm that polarity has a major effect on the reaction rate and hydrogen bond ability of the... 

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... 

Purpose. Variable-Temperature Kinetics has been used to obtain the rate constants of the reaction at various temperatures during one kinetic run. Methods. Pseudo-first-order rate constants for the transesterification of procaine with aliphatic alcohols ethanol, n-propanol and tert-butanol were obtained by the fluorescence spectroscopy using the variable-temperature kinetics (VTK) method. Results. The activation parameters of the reactions were calculated (24-28 kcal.mol-1). The half-life of the procaine decreases in the ethanol solution compared with the other alcoholic solutions in the presence of sodium ethoxide. Conclusions. The investigation time of the reactions is reduced to one-tenth... 

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... 

Structural and intermolecular interactions of solvatochromic probes 4-nitroaniline, 4-nitroanisole, and Reichardts dye were investigated in the binary mixtures of 2-hydroxy ethylammonium formate as an ionic liquid with N,N-dimethyl formamide, dimethyl amine, and dimethyl sulfoxide. Solvatochromic parameters (ETN, normalized polarity parameter; π, dipolarity/polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen -bond donor acidity) were determined in ionic liquid mixtures at 25°C using UV-vis spectroscopy. ETN parameters obtained from absorbance of Reichardt dye within various mixtures of ionic liquid were observed to be higher than predicted values from ideal additive behavior.... 

Structural and molecular-microscopic properties of the solvatochromic probes 4-nitroaniline, 4-nitroanisole, and Reichardt's dye were investigated in binary mixtures of ethylammonium propionate with methanol, ethanol, 1-propanol and 2-propanol. Solvatochromic parameters (α, hydrogen-bond donor acidity; β, hydrogen-bond acceptor basicity; π*, dipolarity/ polarizability; ET N, normalized polarity parameter) in different binary mixtures of ionic liquid with molecular solvents were determined with UV-Vis spectroscopy. The ET N parameters show nearly ideal trends in all solvent mixtures, but the other parameters show different behavior in the mixtures. The πparameters show a negative deviation... 

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... 

Solute-solvent and solvent-solvent interactions were investigated for binary mixtures of an ionic liquid (IL) 2-hydroxy ethylammonium formate as with methanol, ethylene glycol and glycerol. The physicochemical properties of the solvent mixtures at 25 °C, over the whole range of mole fractions, were determined using solvatochromic probes. High normal polarity (ETN) in the alcohol-rich region confirms solute-solvent interactions in this medium. Dipolarity/polarizability (π *) show a different trend to ETN with a positive deviation from ideal behavior in IL-glycerol mixtures. However, these deviations for other solvent mixtures are insignificant. Contrary to what is observed for E TN and π*,... 

The aim of this study is to employ feedback control loops to provide a stable forward dynamics simulation of human movement under repeated position constraint conditions in the environment, particularly during stair climbing. A ten-degrees-of-freedom skeletal model containing 18 Hill-type musculotendon actuators per leg was employed to simulate the model in the sagittal plane. The postural tracking and obstacle avoidance were provided by the proportional—integral—derivative controller according to the modulation of the time rate change of the joint kinematics. The stability of the model was maintained by controlling the velocity of the body's centre of mass according to the desired centre of... 

We use an exact general relativistic model structure within a Friedmann-Robertson-Walker cosmological background based on a Lemaître, Tolman, and Bondi metric to study the gravitational lensing by a cosmological and dynamical structure. Using different density profiles for the model structure, the deviation angle and the time delay through the gravitational lensing has been studied by solving the geodesic equations. The results of these exact calculations have been compared to the thin lens approximation. We have shown that the result for the thin lens approximation based on a modified Navarro-Frenk-White density profile with a void before going over to the Friedmann-Robertson-Walker... 

A heat-transfer model was formulated to determine the distribution of temperature within a bioheap of chalcopyrite of Sarcheshmeh copper mine. Bioleaching employs mixed mesophilic and thermophilic microbes for Cu extraction. Thermophiles are better than mesophiles to dissolve CuFeS2. The solution irrigation and aeration rates were taken into account as the main operational factors. The model was validated by comparing the temperature profiles of test columns with those of bioheap. The model was used to find the optimal ratio of irrigation to aeration. It was found that when the solution was fed at a flow rate of 5 kg/m2 h and air was blown at a flow rate of 7.5 kg/m2 h, the transition from a... 

Reduced graphene oxide (RGO) was used to improve the hydrogen sensing properties of Pd and Pt-decorated TiO2 nanoparticles by facile production routes. The TiO2 nanoparticles were synthesized by sol–gel method and coupled on GO sheets via a photoreduction process. The Pd or Pt nanoparticles were decorated on the TiO2/RGO hybrid structures by chemical reduction. X-ray photoelectron spectroscopy demonstrated that GO reduction is done by the TiO2 nanoparticles and Ti–C bonds are formed between the TiO2 and the RGO sheets as well. Gas sensing was studied with different concentrations of hydrogen ranging from 100 to 10,000 ppm at various temperatures. High sensitivity (92%) and fast response time...