Search results for "reaction rate constant"
showing 10 items of 210 documents
Rate-retarding effects of mixed anionic/non-ionic micelles on the alkaline hydrolysis of the chloropentamminocobalt(III) complex
2006
Abstract Rate data for the alkaline hydrolysis of the chloropentaamminecobalt(III) cation in the presence of mixed micelles composed of (i) anionic sodium decylsulphate (SDeS) and non-ionic dodecylpenta(oxyethylene glycol) monoether (C 12 E 5 ) surfactants and (ii) anionic sodium perfluorooctanoate (SPFO) and non-ionic C 12 E 5 surfactants has been obtained at T 298 K and constant electrolyte concentration 0.08 mol dm −3 ([NaOH] = 0.01 mol dm −3 , [NaClO 4 ] = 0.07 mol dm −3 ) over a wide range of total surfactant concentration ( C t ) and anionic mole fraction ( χ ). The critical micelle concentrations (c.m.c.s) of the mixed micelles have been determined over the entire χ range by means of…
Radikalpolymerisation von methylmethacrylat im gesamten umsatzbereich. Stationäre und instationäre experimente zur bestimmung von wachstums- und abbr…
1989
Free-radical polymerization of methyl methacrylate in bulk at 0°C over the full range of conversion is reported. Details for stationary and non-stationary experiments are described allowing to measure both kinetically relevant ratios fk/ka and kw/ka, f representing radical efficiency, kw rate constants of propagation and ka rate constant of termination. From these ratios the absolute rate constants kw and ka are available. The photochemical decay of the initiator 1,1′-azodicyclohexanenitrile in connection with the rotating-sector technique and observation of the post-effect after stopping the initiator decay were used. The rate of polymerization and the number- and weight-average molar mass…
Über die Elementarreaktionen der radikalischen Polymerisation von Benzylmethacrylat
1973
Durch Kombination stationarer und instationarer Methodik (rotierender Sektor) werden die Absolutwerte der Geschwindigkeitskonstanten von Kettenwachstum und Kettenabbruch von Benzylmethacrylat unter dem Einflus verschieden viskoser Losungsmittel bestimmt. Die Radikalausbeute f hangt von der Viskositat des Losungssystems und der Art der Monomeren, dagegen nicht (oder fast nicht) von der Konzentration des Monomeren und der Geschwindigkeit der Radikalerzeugung ab. Daraus wird geschlossen, das ein merklicher Anteil von Zwillingsrekombinationen auserhalb des primaren Losungsmittelkafigs stattfindet. Die Geschwindigkeitskonstante kw des Kettenwachstums stimmt praktisch uberein mit der des Methylme…
The kinetics of anionic polymerization of styrene in 1,2-dimethoxiethane
2007
Kinetic measurements in a flow apparatus in combination with conductance measurements, permit the determination of the two equilibrium constants Kes and Kdiss* and the three propagation rate constants k(±)c, k(±)s and k(−) as a function of temperature. The great differences in the polymerization rate in various solvents are mainly caused by their influence on the equilibrium constants. The influence of the solvent on the rate constants is not greater than in other chemical reactions.
Influence of inorganic pyrophosphate on the kinetics of muscle pyruvate kinase: a simple nonallosteric feedback model.
2002
Potassium pyrophosphate was used instead of ATP as a model ligand for magnesium cation for the study of effector influence on the kinetics of pyruvate kinase muscle isozyme M1. The pyruvate kinase activation by low concentration of pyrophosphate and inhibition by high concentration of pyrophosphate was considered to be the result of reversible reactions of magnesium cation with pyrophosphate, ADP, ATP, and PEP. The apparent Km and Vm or in some cases the pseudo-first order reaction rate constant (instead of Km and Vm) of pyruvate kinase at any given pyrophosphate concentration were analysed as a function of concentration of free magnesium cation and its complexes with all ligands present in…
Increased dynamic effects in a catalytically compromised variant of Escherichia coli dihydrofolate reductase
2013
Isotopic substitution (15N, 13C, 2H) of a catalytically compromised variant of Escherichia coli dihydrofolate reductase, EcDHFR-N23PP/S148A, has been used to investigate the effect of these mutations on catalysis. The reduction of the rate constant of the chemical step in the EcDHFR-N23PP/S148A catalyzed reaction is essentially a consequence of an increase of the quasi-classical free energy barrier and to a minor extent of an increased number of recrossing trajectories on the transition state dividing surface. Since the variant enzyme is less well set up to catalyze the reaction, a higher degree of active site reorganization is needed to reach the TS. Although millisecond active site motion…
Do dynamic effects play a significant role in enzymatic catalysis? A theoretical analysis of formate dehydrogenase.
2010
A theoretical study of the protein dynamic effects on the hydride transfer between the formate anion and nicotinamide adenine dinucleotide (NAD + ), catalyzed by formate dehydrogenase (FDH), is presented in this paper. The analysis of free downhill molecular dynamic trajectories, performed in the enzyme and compared with the reaction in aqueous solution, has allowed the study of the dynamic coupling between the reacting fragments and the protein or the solvent water molecules, as well as an estimation of the dynamic effect contribution to the catalytic effect from calculation of the transmission coefficient in the enzyme and in solution. The obtained transmission coefficients for the enzyme…
Molecular structure of the compound [Rh2(O2CCH3)3{(C6H4)P(BrC6H4-1,2)(C6H5)} · (HO2CCH3)2].Kinetic study of the exchange reaction of acetate groups w…
1993
Abstract The compound [Rh 2 (O 2 CCH 3 ) 3 {(C 6 H 4 )P(BrC 6 H 4 -1,2) (C 6 H 5 )} · (HO 2 CCH 3 ) 2 ] has been isolated in high yield from the thermal reaction of dirhodium tetraacetate and the phosphine P(BrC 6 H 4 -1,2) (C 6 H 5 ) 2 in acetic acid. The structure of this compound has been determined by X-ray diffraction; it crystallizes in the P 1 (triclinic) space group and contains three acetate groups bridging a Rh 2 4+ unit the RhRh distance being 2.432(1)A; the fourth bridging ligand is an ortho -bromophenyldiphenylphosphine metallated at one of the ortho positions of the unsubstituted phenyl rings. Two molecules of acetic acid occupy the axial coordination positions. Stepwise exch…
A deep insight into the mechanism of the acid-catalyzed rearrangement of the Z-phenylhydrazone of 5-amino-3-benzoyl-1,2,4-oxadiazole in a non-polar s…
2010
The conversion of the Z-phenylhydrazone of 5-amino-3-benzoyl-1,2,4-oxadiazole (1a) into the relevant 1,2,3-triazole (2a) has been quantitatively studied in toluene in the presence of several halogenoacetic acids (HAAs, 3a–h). Again, the occurrence of two reaction pathways has been pointed out: they require one or two moles of acid, respectively, thus repeating the situation previously observed in the presence of trichloroacetic acid. The observed rate constant ratios (kIII/kII) are only slightly affected by the nature of the acid used. To gain a deeper insight into the action of the acids used we have measured the association constants of the HAAs (3a–h) with 4-nitroaniline (4) in toluene. …
Role of Halide Ion in the Mechanism of Protonolysis of the Pt-C Bond in Pt(II) Alkyl and Aryl Complexes.
1985
Abstract A mechanistic study is described for the electrophilic cleavage of the Pt C σ bond in complexes cis -[PtPh 2 (PEtPh 2 ) 2 ] and trans -[PtXR(PEt 3 ) 2 ] (X = Cl and Br, R = Me, Et, n-Pr, n-Bu, CH 2 Ph) by the proton in the presence of halide ions in aqueous methanol (MeOH/H 2 O, 91v/v) which yields cis -[PtClPh(PEtPh 2 ) 2 ] and trans -[PtX 2 (PEt 3 ) 2 ], respectively. The reactions are first-order in substrate for both systems and the general bivariate rate law k obs = [H + ]{ k H + k x K [[X − ]}/(1 + K [[X − ]) is obeyed. The proposed mechanism involves a fast pre-equilibrium formation (K) of a platinum(II) anionic intermediate via interaction of the halide with the square-plan…