Search results for "Order of reaction"

1986

The kinetics of polyamidation was investigated for the reaction of diphenyl terephthalate as activated diester with trimethylhexamethylenediamine (1 : 1 mixture of 2,2,4- and 2,4,4-trimethyl isomers) in dimethyl sulfoxide. The good solubility of the resulting polyamide (Trogamid®(poly(iminoterephthaloylimino-x,y,z-trimethylhexamethylene))) assured a reaction in which all reactants, especially the polyamide, were soluble. The conversion was followed by analysis of the phenol set free and by measuring the number-average degree of polymerization Pn of the polyamide. The reaction obeyed an overall second order with the principle of equal reactivity of functional groups fulfilled for Pn ≿ 16. De…

The kinetics of the olivine dissolution under the extreme conditions of nano-silica production

2015

Abstract This article addresses the kinetics of the dissolution of olivine for nano-silica production at extreme conditions. The extreme conditions are pH values between −0.7 and 1, temperature between 50 and 90 °C, solid content around 250 g/L and percentage dissolved between 80% and 99%. This work is structured in 3 parts: (1) chemical and mineralogical characterization of the dunites employed; (2) mechanism of the olivine dissolution focusing on the possible resistances to the transport; and (3) determination of the kinetic parameters kT and n. The results shown here demonstrate that: (1) the limiting step of this process is not the diffusion through a silica layer but the surface reacti…

Effect of Lithium Perchlorate on the Kinetics of the Anionic Polymerization of Methyl Methacrylate in Tetrahydrofuran

1999

The kinetics of the anionic polymerization of methyl methacrylate in the presence of lithium perchlorate (LiClO 4 ) are investigated in THF using 1,1-diphenylhexyllithium as initiator in a flow-tube reactor between -30 and 0 °C. The rate constants of propagation determined in the presence of LiClO 4 are lower than those obtained in the absence of the salt, similar to the effect observed for LiCl. For propagation, the reaction order with respect to active center concentration is found to be 0.5 in both cases, which indicates that LiClO 4 does not effectively perturb the aggregation of the enolate ion pair. The formation of various mixed aggregates is proposed. The polydispersity index of the…

Synthesis, characterization and thermal degradation of 8-hydroxyquinoline–guanidine–formaldehyde terpolymer

2007

Abstract Terpolymer (8-HQGF) has been synthesized using the monomers 8-hydroxyquinoline, guanidine, formaldehyde in 1:1:2 molar proportions. The structure of 8-HQGF terpolymer has been elucidated on the basis of elemental analysis and various physicochemical techniques, i.e. UV–Visible, FTIR–ATR and 1 H NMR spectroscopy. Detailed thermal degradation study of the new terpolymer has been carried out to ascertain its thermal stability. Thermal degradation curve is discussed which shows two decomposition steps (265–475 °C and 540–715 °C). Sharp–Wentworth and Freeman–Carroll methods have been used to calculate activation energies and thermal stability. The activation energy ( E a ) calculated by…

Trapping AsPh3 via reaction with NiS/γ-Al2O3 in the presence of H2: Reaction mechanism and kinetics

2021

International audience; Removal of As from petroleum feedstocks is an important process which can be realized using As trapping mass containing supported nickel sulfide. In order to understand the mechanism of the trapping we studied the reaction of AsPh3 with NiS/γ-Al2O3 in the presence of H2 in a batch reactor in toluene solution at 230 °C. This reaction results in formation of NiAs, benzene and H2S. Also, the intermediate species, thiophenol and diphenylsulfide, were observed. Despite formation of NiAs layer in the course of reaction, the rate of AsPh3 decomposition is not affected by the solid state diffusion up to ∼ 50 % of nickel conversion. The rate determining step in these conditio…

A study of the diels-alder reaction of 3-oxabicyclo[3.3.0]oct-1(5)-ene-2,4-dione with cyclopentadiene and some related dienes

1984

Abstract The reaction of 3-oxabicyclo[3.3.0]oct-l(5)ene-2,4-dione, 2, with cyclopentadiene, 3, 5,5-diethoxycyclopentadiene, 4, and 6,6-dimethylfulvene, 5, is studied. Reaction of 2 and 3 yields the expected endo-adduct, while reaction of 2 and 5 gives a mixture of the endo- and exo-adducts whose ratio is slightly dependent on the reaction conditions. Attractive electrostatic interactions in the transition state leading to the exo-adduct can explain the absence of endo stereoselectivity in the last reaction. Steric factors seem to be responsible for the absence of reaction between 2 and 4. The analysis of the 13C NMR spectra of these adducts and some derived compounds confirms the tentative …

Studies on the Mechanism of Inhibition by Phosphinothricin of Glutamine Synthetase Isolated from Triticum aestivum L.

1986

Summary The activity of glutamine synthetase (EC 6.3.1.2) isolated from roots and leaves of wheat is strongly inhibited by phosphinothricin. As revealed by gel filtration and kinetic studies the mechanism of inhibition appears to be irreversible. The results indicate that the rate limiting step of the reaction of the inhibitor with the chloroplast glutamine synthetase is not the initial, but the following reaction. However, of root glutamine synthetase the irreversible inhibition follows a second order reaction depending on the concentration of the enzyme and of phosphinothricin and the rate limiting step is the formation of the initial enzyme-inhibitor complex. According to the kinetic dat…

The effect of TMEDA on the kinetics of the anionic polymerization of methyl methacrylate in tetrahydrofuran using lithium as counterion

2000

The kinetics of the anionic polymerization of methyl methacrylate in presence of N,N,N', -tetramethylethylenediamine (TMEDA) in THF are investigated using 1,1-diphenyl-hexyllithium as initiator in a temperature range between -20°C and 0°C in a flow-tube reactor. The rate constants of propagation determined in the presence of TMEDA are compared to those obtained in the absence of a chelating agent. For propagation, the reaction order with respect to active centers is found to be 0.5 in both cases which indicates that the chelation of the lithium cation does not effectively perturb the aggregation of the enolate ion pair. Both the rate constants of propagation via non-aggregated ion pairs, k …

1977

Methacryloyloxyalkyltrimethylammonium chlorides (1a–c) with different alkyl chain lengths were synthesized and polymerized radically with 4,4′-azobis(4-cyanovalerianic acid) and K2S2O8 as initiators. With K2S2O8 as initiator, reaction orders of 0,5 and 1 with respect to initiator and monomer, were found. For the ionic monomers with longer alkyl chains the ratio of rate constants kp(2fkd/kt)0,5 was determined over a wide concentration range. It was found that with decreasing monomer concentration the ratio of rate constants increases, which is caused by a diminished termination rate because of an increased electrostatic repulsion of the ionic polymer radicals in dilute solution (increase of …

Translocation of Cations During Sorption of Copper in the System Solution - Algae (Spirogyra sp.)/Translokacja Kationów Podczas Procesu Sorpcji Miedz…

2014

Zbadano kinetykę procesu sorpcji kationów miedzi w glonach Spirogyra sp. oraz towarzyszące mu procesy sorpcji kationów wodorowych i procesy uwalniania do roztworu kationów związanych w glonach: Na+, Mg2+, K+ i Ca2+. Stwierdzono, że w układzie statycznym, przy stałym stosunku masy glonów do objętości roztworu, procesy te zachodzą równocześnie, przy czym należy przypuszczać, że ilość uwalnianych soli ma wpływ na parametry heterofazowej równowagi wymiany jonowej. W warunkach prowadzenia eksperymentu ilość uwolnionych kationów była blisko 10-krotnie większa niż ilość kationów sorbowanych. Porównano parametry równowagi wyznaczone z modelu reakcji pseudo-drugiego rzędu z parametrami uzyskanymi po…