Search results for "Reaction rate"
showing 10 items of 346 documents
Mechanisms of cement hydration
2011
Abstract The current state of knowledge of cement hydration mechanisms is reviewed, including the origin of the period of slow reaction in alite and cement, the nature of the acceleration period, the role of calcium sulfate in modifying the reaction rate of tricalcium aluminate, the interactions of silicates and aluminates, and the kinetics of the deceleration period. In addition, several remaining controversies or gaps in understanding are identified, such as the nature and influence on kinetics of an early surface hydrate, the mechanistic origin of the beginning of the acceleration period, the manner in which microscopic growth processes lead to the characteristic morphologies of hydratio…
On the role of interfacial hydrogen bonds in "on-water" catalysis.
2014
Numerous experiments have demonstrated that many classes of organic reactions exhibit increased reaction rates when performed in heterogeneous water emulsions. Despite enormous practical importance of the observed "on-water" catalytic effect and several mechanistic studies, its microscopic origins remains unclear. In this work, the second generation Car-Parrinello molecular dynamics method is extended to self-consistent charge density-functional based tight-binding in order to study "on-water" catalysis of the Diels-Alder reaction between dimethyl azodicarboxylate and quadricyclane. We find that the stabilization of the transition state by dangling hydrogen bonds exposed at the aqueous inte…
High accuracy [sup 18]O(p,α)[sup 15]N reaction rate in the 8⋅10[sup 6]–5⋅10[sup 9] K temperature range
2011
The 18O(p,α)15N reaction is of great importance in several astrophysical scenarios, as it influences the production of key isotopes such as 19F, 18O and 15N. In this work, a high accuracy 18O(p,α)15N reaction rate is proposed, based on the simultaneous fit of direct measurements and of the results of a new Trojan Horse experiment. In particular, we have focused on the study of the broad 660 keV 1/2+ resonance. Since Γ∼100–300 keV, it strongly influences the nearly‐zero‐energy region of the cross section by means of the low‐energy tail of the resonant contribution and dominates the cross section at higher energies. Here we provide a factor of 2 larger reaction rate above T∼0.5 109 K based ov…
Data Treatment in Kinetics
2000
Chemical kinetics is an important part of chemistry devoted to study how reactions proceed and quantify the rate of the process. The reaction mechanism is the chemical model that describes how the chemical change occurs. From the proposed mechanism, a mathematical model can be obtained to explain the evolution of the chemical species with time. In many cases, the mechanism can be simplified to a single rate law that relates the reaction rate with concentrations. In the last decades, the study of kinetic systems has benefited from the development of instrumentation, the increasing availability of specialized computer software, and the advances in data treatment techniques. A comprehensive re…
A theoretical and experimental study of the formation mechanism of 4-X-chalcones by the Claisen–Schmidt reaction
2000
Abstract A theoretical and experimental study on the formation of 4-X-chalcones (X=H, Cl, F, OCH3, N(CH3)2) was carried out by the Claisen–Schmidt reaction. The influence of pH and temperature was analyzed. Under the adopted experimental conditions 4-X-chalcones were the only reaction products. In the theoretical study, the thermodynamic magnitudes and the reactivity indexes calculated with the AM1 method were used. The mechanism of Nayak and Rout was analyzed critically and a new mechanism was proposed, characterized by: (1) rapid nucleophilic attack of the catalyst (OH−) on the carbon atom of the methyl group of acetophenone; (2) attacks of the acetophenonate ion on the carbon atom of the…
Photocatalytic degradation of 4-Nitrophenol by g-C3N4-MCy: Mechanism study and kinetic modeling
2021
Abstract A graphitic carbon nitride (g-C3N4-MCy) photocatalyst was prepared by thermal condensation of melamine and cyanuric acid with equal proportions. The photocatalyst was characterized by Fourier transform infrared spectroscopy (FTIR), Specific surface area (SSA), X-ray diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM), Transmission electron microscope (TEM), and DRS–UV–Vis spectroscopic methods. We studied the photo-degradation kinetics of 4-nitrophenol using a g-C3N4-MCy. Four parameters were applied including initial concentration of 4-nitrophenol, amount of catalyst, dissolved oxygen content, and photon flux. The reaction rate constant was shown to be correlate…
Understanding the mechanism of the Povarov reaction. A DFT study
2014
The molecular mechanism of the Povarov reaction in acetonitrile has been studied at the MPWB1K/6-311G** level of theory. This reaction follows a domino process that comprises two sequential reactions: (i) a Lewis acid catalysed aza-Diels–Alder (A-DA) reaction between a N-aryl imine and a nucleophilic ethylene yielding a formal [4 + 2] cycloadduct; (ii) a stepwise 1,3-hydrogen shift at this intermediate affording the final tetrahydroquinoline. At this computational level, the Lewis acid catalysed A-DA reaction presents a two-step mechanism as a consequence of the large stabilisation of the corresponding zwitterionic intermediate. Our study allows establishing that the N-aryl substituent has …
A molecular electron density theory (MEDT) study of the role of halogens (X2= F2, Cl2, Br2and I2) on the aza-Michael-addition reactions
2020
Using the Molecular Electron Density Theory (MEDT), a set of uncatalyzed and X2 molecule-catalyzed (X2 = F2, Cl2, Br2, or I2) aza Michael addition reactions (aza-MARs) between pyrrolidine (PYR) and methyl acrylate (MA) have been studied in the gas phase and in dichloromethane (DCM) medium from the kinetics and molecular mechanism aspects. Analysis of the conceptual DFT reactivity indices indicates that the coordination of the X2 molecules to the oxygen of the MA's carbonyl group increases both the softness and the electrophilic character of MA, thus explaining the catalytic role of the X2 molecules. The nucleophilic attack of the nitrogen of PYR on the MA's β conjugated carbon is the rate-d…
Kinetics and equilibrium in insulin radioimmunoassay.
2002
The kinetics of insulin reaction has been studied with its specific antibody immobilized on the inner wall of the reaction tube; the radioimmunoanalytical determination of such a substance is based on the reaction. Independent variables were labelled and unlabelled insulin concentrations, temperature, viscosity, and the medium's ionic strength. Biexponential kinetics was found to be dependent on the concentrations fitted to the models discussed in the paper. The effect of temperature shows activation parameters similar to the viscous flow energy of water, which suggests that the reaction is diffusion-controlled. The results of the viscosity analysis points at the clearly negative influence …
Chemical Reactivity in AOT Microemulsions: Kinetics of Water Replacement in a Square-Planar Palladium(II) Aquo Complex by Monoalkylthioureas
1998
The kinetics of water replacement in the cationic palladium(II) aquo complex [Pd(Et4dien)(H2O)]2+, where Et4dien = Et2N(CH2)2NH(CH2)2NEt2, by thiourea, methylthiourea, and ethylthiourea have been studied at 25.0 °C in heptane−AOT−water microemulsion over a wide range of the molar ratio R (=[H2O]/[AOT]) at the constant surfactant concentration of 0.13 mol dm-3. The reaction rates are significantly higher in microemulsions than in bulk water and decrease rapidly as the parameter R increases. The kinetic data, interpreted quantitatively by applying the pseudophase model to the microemulsion, indicate that there is a weak partitioning of the nucleophiles between the water core and the AOT inter…