Search results for " rate constant"
showing 10 items of 220 documents
ISomerization of xylene: MINDO/3 study of the cyclization of benzenium cation into bicyclo[3.1.0]hexenyl cation
1989
Abstract A MINDO/3 study of thermal electrocyclic closing of the benzenium cation to form a bicyclo[3.1.0]hexenyl cation is presented. The calculated mechanism discusses the possibility of cyclization of xylenium cations on a silica catalyst or in superacid media. The structure and energy of the transition state, the enthalpies of isomerization and barriers of activation were calculated for the following processes: isomerization of 2,6-dimethylbenzenium cation into 2,6-dimethylbicyclo[3.1.0]hexenyl cation, isomerization of 2,4-dimethylbenzenium cation into 2,4-dimethylbicyclo[3.1.0]-hexenyl cation, and isomerization of benzenium cation into bicyclo[3.1.0]-hexenyl cation. Equilibrium and kin…
Photokinetic examination of (Z,E,E)-4,4′-distyrylazobenzene
1995
Abstract 4,4′-Distyrylazobenzenes demonstrate a photokinetic equilibrium and a superimposed thermal backward reaction in which the absorption coefficient of one of the partners in the equilibrium is principally unknown. Using the dependence of the photostationary state on the irradiation intensity, the photochemical quantum yields ϕ 1 A and ϕ 2 B were determined, as well as the thermal rate constant k , as a function of the irradiation and observation wavelengths. Experimental difficulties and the wavelength dependence of ϕ 1 A and ϕ 2 B are discussed.
The reaction of 2-methoxy-3-nitrothiophene with N-benzylmethylamine in methanol
1990
The kinetics of the title reaction has been studied in methanol as a function of amine and methoxide ion concentrations. The kinetic coefficients obtained point out that the reaction is catalysed by methoxide through a SB catalysis mechanism.
The effect of excipients on the stability and phase transition rate of xylazine hydrochloride and zopiclone
2015
The compatibility of thermodynamically unstable polymorph of two active pharmaceutical compounds (xylazine hydrochloride form X and zopiclone form C) with different excipients was investigated. The effects of the excipient and its amount in the sample on the thermal properties and possible chemical interactions were studied. The most commonly used excipients in the pharmaceutical industry - calcium carbonate, lactose hydrate, cellulose, magnesium stearate hydrate and calcium stearate hydrate were selected for this study. The dependence of the phase transition rate from an unstable to a more stable polymorph on the excipients and their amounts in the initial sample was analysed at 80°C, and …
First-Principles Computed Rate Constant for the O + O 2 Isotopic Exchange Reaction Now Matches Experiment
2018
We show, by performing exact time-independent quantum molecular scattering calculations, that the quality of the ground electronic state global potential energy surface appears to be of utmost importance in accurately obtaining even as strongly averaged quantities as kinetic rate constants. The oxygen isotope exchange reaction, 18O + 32O2, motivated by the understanding of a complex long-standing problem of isotopic ozone anomalies in the stratosphere and laboratory experiments, is explored in this context. The thermal rate constant for this key reaction is now in quantitative agreement with all experimental data available to date. A significant recent progress at the frontier of three rese…
Blue-luminescent organic lead bromide perovskites: highly dispersible and photostable materials
2015
The preparation of a blue-luminescent and photostable organic–inorganic hybrid perovskite with an X-ray powder diffraction spectrum consistent with a two-dimensional inorganic framework is reported. This perovskite can be produced with a high reaction yield and valuable optical properties, such as luminescence quantum yield over 20%, radiative rate constant of up to 80 × 106 s−1, and high photostability under UV light. This material remains stable as a solid, is toluene-dispersible, and can be reverted reversibly into its precursors by using dimethylformamide (DMF). Moreover, the DMF dispersion can be injected into toluene to produce a nanomaterial or be used to prepare films by spin-coatin…
Properties of trialkylamines as catalysts of resoles synthesis
2000
A series of the syntheses of phenol–formaldehyde resoles was carried out in the presence of trimethyl-, triethyl-, tripropyl-, and tributylamines and sodium hydroxide as catalysts for this process. The rate constants were calculated for the partial reactions identified in the synthesis. Also, the performance properties of the resins obtained and the hardened resin samples were estimated in simple tests. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 898–902, 2000
Reversibility and Diffusion in Mandelythiamin Decarboxylation. Searching Dynamical Effects in Decarboxylation Reactions
2012
Decarboxylation of mandelylthiamin in aqueous solution is analyzed by means of quantum mechanics/molecular mechanics simulations including solvent effects. The free energy profile for the decarboxylation reaction was traced, assuming equilibrium solvation, while reaction trajectories allowed us to incorporate nonequilibrium effects due to the solvent degrees of freedom as well as to evaluate the rate of the diffusion process in competition with the backward reaction. Our calculations that reproduce the experimental rate constant show that decarboxylation takes place with a non-negligible free energy barrier for the backward reaction and that diffusion of carbon dioxide is very fast compared…
Entropy-controlled diastereoselectivity in the photocyclization of rigid derivatives of o-allylaniline.
2002
Two rigid derivatives of o-allylaniline, namely 8-allyl-2-phenyl-1,2,3,4-tetrahydroquinoline (1b) and 7-(trans-2-cinnamyl)-2-methylindoline (1c), have been chosen as suitable systems to study the potential stereoselectivity of the photocyclization process. Photolysis of 1b leads to a mixture of diastereomeric lilolidines 4 (trans/cis), while 1cproduces a mixture of 4 (trans/cis) and the tetrahydropyrrolo[3,2,1-hi]indole derivatives 5 (trans/cis). To disclose whether the diastereoselectivity could be entropy dependent, photolysis of 1b and 1c has been performed at several temperatures. In both cases, linear relationships have been observed when ln(k(t)/k(c)) (the relative reaction rate const…
Toward more realistic viscosity measurements of tyre rubber–bitumen blends
2014
AbstractThe measurement of rheological properties of the tyre rubber bitumen blends is often challenging due to presence of suspended tyre rubber’s crumbs. Furthermore, the phase separation during the course of measurements makes the viscosity of these non-homogeneous blends difficult to ascertain. In this study, a new dual helical impeller was designed and manufactured to be used with a rotational viscometer in order to have a real-time control of the viscosity while performing a laboratory mixing of the blends. Layer based manufacturing techniques showed to be a convenient method to produce complex shaped impeller prototypes before manufacturing the more expensive stainless steel assembly…