Structural reasons for the formation of multicomponent products and the influence of high pressure

Author(s):  
Krzysztof A. Konieczny ◽  
Julia Bąkowicz ◽  
Damian Paliwoda ◽  
Mark R. Warren ◽  
Arkadiusz Ciesielski ◽  
...  

(S)-(−)-1-Phenylethanaminium 4-(2,4,6-triisopropylbenzoyl)benzoate (S-PEATPBB) undergoes a photochemical reaction in its crystalline form upon UV irradiation and forms three different products: the first product is the result of a Yang cyclization with the participation of the δ-H atom of o-isopropyl (product D) and the second and third products are obtained via a Norrish–Yang reaction with the involvement of the γ-H atom of 2-isopropyl (product P) and 6-isopropyl (product Z). These products are formed in different proportions (D > P >> Z). The path and kinetics of the reaction were monitored step-by-step using crystallographic methods, both under ambient and high-pressure conditions. The reactivity of S-PEATPBB depends strongly on the geometry of the reaction centre and the volume of the reaction cavity. Due to the geometrical preferences making the cyclization reaction easier to proceed, product D dominates over the other products, while the formation of product Z becomes difficult or almost impossible at high pressure. The reaction proceeds with an increase of the unit-cell volume, which, suppressed by high pressure, results in a significant decrease of the reaction rate. The crystal lattice of S-PEATPBB shows high elasticity. The quality of the partially reacted crystal remains the same after decompression from 0.75 GPa to 0.1 MPa.

Author(s):  
M.A. Egyan ◽  

The article shows studies characterizing the quality of the squeeze: the mechanical composition of the squeeze is determined, the structural moisture of each component is determined, the sugar content in the formed process of sedimentation of the juice and its acidity are determined refractometrically. The kinetics of anthocyanins extraction was determined in two ways, the solids content in the extract was calculated, and the reaction rate constants of the extraction process and the efficiency coefficient of ultrasonic amplification of the extraction process speed were calculated.


2019 ◽  
Vol 15 (5-6) ◽  
Author(s):  
H. Hadiyanto ◽  
Marcelinus Christwardana ◽  
Meiny Suzery ◽  
Heri Sutanto ◽  
Ayu Munti Nilamsari ◽  
...  

AbstractPhycocyanin is a natural substance that can be used as an antioxidant and food colorant. The quality of phycocyanin deteriorates when it is exposed to heat, and such deterioration is evidenced by decreases in its antioxidant activity and color. Encapsulation, which introduces a coating material over a substance of interest, has been applied to prevent changes in substance quality. The objective of the present research is to evaluate the kinetics of thermal degradation of phycocyanin coated with carrageenan or chitosan. Encapsulated phycocyanin samples were exposed to temperatures of 40, 50, or 60 °C for 90 min, and kinetics of the resulting degradation was evaluated to determine changes in sample quality. The results showed that the thermal degradation of encapsulated phycocyanin at 40–60 °C follows first-order reaction kinetics with reaction rate constants (k) of 4.67–9.17 × 10–5 s-1 and 3.83–7.67 × 10–5 s-1 for carrageenan and chitosan, respectively, and that the k of encapsulated phycocyanin is slower than that obtained from samples without the coating materials (control). Encapsulation efficiencies (EE) of 68.66 % and 76.45 %, as well as loading capacities of 45.28 % and 49.16 %, were, respectively, obtained for carrageenan and chitosan.


1938 ◽  
Vol 16b (8) ◽  
pp. 260-272 ◽  
Author(s):  
E. W. R. Steacie ◽  
I. E. Puddington

The kinetics of the thermal decomposition of isobutane has been investigated over an initial pressure range of from 5 to 60 cm., and at temperatures from 522 to 582 °C. The initial first order rate constants at high pressures are given by[Formula: see text]The results are in general agreement with those obtained by previous investigators. The reaction rate falls off with diminishing pressure, and the first order rate constants in a given run diminish strongly as the reaction proceeds. This behavior is similar to that of n-butane.Analyses of the products of the reaction were made at various stages, temperatures, and initial pressures by low-temperature distillation in a still of the Podbielniak type. The initial products were found by extrapolation to be H2, 35; CH4, 14; C2H4, 0.9; C2H6, 0.9; C3H6, 14; and C4H8, 35%. The results are compared with those of other workers.


1970 ◽  
Vol 48 (22) ◽  
pp. 3487-3490 ◽  
Author(s):  
J. Brown ◽  
George Burns

Kinetics of BrO decomposition was studied between 293 and 673 °K using the technique of kinetic spectroscopy. At 293 °K the reaction rate is second order with respect to BrO and is independent of [Br2], [O2], and total pressure of diluent gas. The activation energy for decomposition obtained from rate measurements between 293 and 450 °K is 0.65 ± 0.05 kcal/mole. Above 450 °K this activation energy appears to increase to 4.5 kcal/mole. It is shown that, although kinetically the ClO and BrO decompositions are similar, the mechanism for BrO decomposition below 450 °K is much simpler than that of ClO. The reaction proceeds, most likely, via one step: 2 BrO → 2 Br + O2, with Br2O2 being an activated complex, which has either linear or staggered configuration. ClO and BrO decomposition is compared with [Formula: see text] reaction.


1990 ◽  
Vol 04 (01) ◽  
pp. 29-35 ◽  
Author(s):  
A. A. STEPANOV ◽  
N. G. HAINOVSKY ◽  
Yu. T. PAVLYUKHIN ◽  
A. I. RYKOV

Kinetics of oxygen absorption in YBa 2 Cu 3 O 6+x has been described. Experiments were performed in the high pressure reactor with constant volume in the temperature range of 150–700°C and oxygen pressure 1.4–10.7 atm. Two stages of oxygen absorption in tetraphase have been discovered. The first is related to the formation of a solid solution of oxygen in Cu(I) layers with the activation energy 0.07 ± 0.01 eV . The second one is oxygen diffusion in the system of short disordered chains ( Cu − O )n with the activation energy 0.30 ± 0.01 eV . Growths of chains and their interaction during the second stage results in the formation of ortho-phase accompanied by further decrease of the reaction rate. Structure-chemical reasons for the multistage mechanism of oxygen absorption are discussed.


2019 ◽  
Author(s):  
Milad Narimani ◽  
Gabriel da Silva

Glyphosate (GP) is a widely used herbicide worldwide, yet accumulation of GP and its main byproduct, aminomethylphosphonic acid (AMPA), in soil and water has raised concerns about its potential effects to human health. Thermal treatment processes are one option for decontaminating material containing GP and AMPA, yet the thermal decomposition chemistry of these compounds remains poorly understood. Here, we have revealed the thermal decomposition mechanism of GP and AMPA by applying computational chemistry and reaction rate theory methods. <br>


2020 ◽  
pp. 99-104
Author(s):  
S.A. Zaydes ◽  
A.N. Mashukov ◽  
T.Ya. Druzhinina

The contact belt of the gate assembly is the main part of high pressure fittings. The serviceability of the fittings assembly as whole depends on the air-tightness and quality of the mating surfaces. The technology of diamond burnishing allows to increase the interface of the nodes by red ucing the surface roughness of the metal-to-metal seal. The real experience for improving of the fittings contact belt due to the use of diamond burnishing of the nozzles seats and the conical surface of the rods.


1989 ◽  
Vol 21 (6-7) ◽  
pp. 435-442 ◽  
Author(s):  
B. Döll

Silica suspensions (pH = 6.8) and three different cationic polymers were used to study the kinetics of charge neutralization by polyelectrolyte adsorption. The experiments were performed in a continuous flow pipe reactor under steady state turbulent flow conditions. The charge neutralization was monitored by electrophoretic mobility (EPM) measurements of the suspended particles as a function of time after polyelectrolyte audition. The results show the dependency of the destabilization reaction rate on flow and polymer characteristics.


1986 ◽  
Vol 51 (12) ◽  
pp. 2786-2797
Author(s):  
František Grambal ◽  
Jan Lasovský

Kinetics of formation of 1,2,4-oxadiazoles from 24 substitution derivatives of O-benzoylbenzamidoxime have been studied in sulphuric acid and aqueous ethanol media. It has been found that this medium requires introduction of the Hammett H0 function instead of the pH scale beginning as low as from 0.1% solutions of mineral acids. Effects of the acid concentration, ionic strength, and temperature on the reaction rate and on the kinetic isotope effect have been followed. From these dependences and from polar effects of substituents it was concluded that along with the cyclization to 1,2,4-oxadiazoles there proceeds hydrolysis to benzamidoxime and benzoic acid. The reaction is thermodynamically controlled by the acid-base equilibrium of the O-benzylated benzamidoximes.


Sign in / Sign up

Export Citation Format

Share Document