Search results for "reaction rate constant"

Equilibrium and kinetic studies on complex formation and decomposition and the movement of Cu2+metal ions within polytopic receptors

2013

Potentiometric studies carried out on the interaction of two tritopic double-scorpiand receptors in which two equivalent 5-(2-aminoethyl)-2,5,8-triaza[9]-(2,6)-pyridinophane moieties are linked with 2,9-dimethylphenanthroline (L1) and 2,6-dimethylpyridine (L2) establish the formation of mono-, bi- and trinuclear Cu(2+) complexes. The values of the stability constants and paramagnetic (1)H NMR studies permit one to infer the most likely coordination modes of the various complexes formed. Kinetic studies on complex formation and decomposition have also been carried out. Complex formation occurs with polyphasic kinetics for both receptors, although a significant difference is found between bot…

Metallic lead recovery from lead-acid battery paste by urea acetate dissolution and cementation on iron

2009

Abstract A suitable hydrometallurgical and environmentally friendly process was studied to replace the currently used practices for recycling lead-acid batteries via smelting. Metallic lead was recovered by cementation from industrial lead sludge solutions of urea acetate (200 to 500 g/L) using different types of metallic iron substrates (nails, shaving or powder) as reducing agents. Under specific operating conditions, up to 99.7% of lead acid battery paste, mainly composed of PbSO4, PbO2 and PbO·PbSO4 species, was converted to metallic lead.. The conversion of the metallic lead and rate of the cementation reaction were strictly dependent on the type of iron substrate used as the reductant…

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…

Synthesis and structure of the incomplete cuboidal clusters [W3Se4H3(dmpe)3]+, [W3Se4H3−x(OH)x(dmpe)3]+and [W3Se4(OH)3(dmpe)3]+, and the mechanism of…

2004

The novel incomplete cuboidal cluster [W3Se4H3(dmpe)3](PF6), [1](PF6), has been prepared by reduction of [W3Se4Br3(dmpe)3](PF6) with LiBH4 in THF solution. The trihydroxo complex [W3Se4(OH)3(dmpe)3](PF6), [2](PF6), was obtained by reacting [W3Se4Br3(dmpe)3](PF6) with NaOH in MeCN–H2O solution. The complexes [1](PF6) and [2](PF6) were converted to their BPh4− salts by treatment with NaBPh4. Recrystallisation of [1](BPh4) in the presence of traces of water affords the mixed dihydride hydroxo complex [W3Se4H2(OH)(dmpe)3](BPh4). The crystal structures of [1](BPh4), [2](BPh4) and [W3Se4H2(OH)(dmpe)3](BPh4) have been resolved. Although the [1]+ trihydride does not react with an excess of halide s…

Analyzing the uniqueness of the rate constants calculated from complex kinetic systems: A study of the hydrolysis of ciclohexanecarbonitriles

1999

Kinetik und Radikalausbeute beim Zerfall tertiärer Hyponitrite

1971

Der thermische Zerfall von Dicumylhyponitrit (1a) ist eine Reaktion erster Ordnung mit einer Aktivierungsenthalpie von 27.3 keal/Mol und einer Aktivierungsentropie von 8.5 cal/Mol·Grad in Isooctan. Die Radikalausbeute fur 1a betragt 84%, fur Di-tert.-butylhyponitrit 92%. Die Zerfallskonstanten substituierter Dicumylhyponitrite gehorchen bei Verwendung der σ+-Werte der Hammett-Beziehung mit σ=+ +0.34. Kinetic and Radical Efficiency for the Decomposition of Tertiary Hyponitrites The thermal decomposition of dicumylhyponitrite (1a) is a first order reaction with an activation enthalpy of 27.3 kcal/mole and an activation entropy of 8.5 e. u. in isooctane. The efficiency of radical formation is …

Dinuclear Zn II Complexes of Polydentate Polyamines as Minimalist Models of Hydrolytic Reactions

2004

The synthesis of the novel macrocycle 2,6,9,12,16-pentaaza[17](2,9)(1,10)phenanthrolinophane (L3) is reported. Speciation studies on the systems ZnII−L3 and ZnII−L2 (L2 =2,6,10,13,17,21-hexaaza[22]metacyclophane) performed in aqueous solution show the formation of mono- and dinuclear ZnII complexes. In the two systems, the dinuclear complexes readily hydroxylate, with the hydroxo species being the main ones in solution at relatively low pH values. This feature makes these complexes promising hydrolytic agents for carboxy and phosphate esters. The hydrolytic ability of the L1−L3 dinuclear complexes toward the carboxy and phosphate ester bond was tested by addition of p-nitrophenyl acetate (N…

Electrochemical and Electronic Structure Investigations of the [S3N3]• Radical and Kinetic Modeling of the [S4N4]n/[S3N3]n (n = 0, −1) Interconversion

2009

Voltammetric studies of S4N4 employing both cyclic (CV) and rotating disk (RDE) methods in CH2Cl2 at a glassy carbon electrode reveal a one-electron reduction at −1.00 V (versus ferrocene/ferrocenium), which produces a second redox couple at −0.33 V, confirmed to be the electrochemically generated [S3N3]− by CV studies on its salts. Diffusion coefficients (CH2Cl2/0.4 M [nBu4N][PF6]) estimated by RDE methods: S4N4, 1.17 × 10−5 cm2 s−1; [S3N3]−, 4.00 × 10−6 cm2 s−1. Digital simulations of the CVs detected slow rates of electron transfer for both couples and allowed for a determination of rate constants for homogeneous chemical reaction steps subsequent to electron transfer. The common paramet…

Kinetic treatment of slow initiation in living carbocationic polymerization and investigation of benzyl halides as initiators for the polymerization …

1998

In contrast to earlier conclusions it is demonstrated that kinetic analysis of incremental monomer addition (IMA) experiments for living carbocationic polymerizations with slow initiation leads only to the ratio of apparent rate constants of initiation and propagation. The apparent rate constants depend on the true (bimolecular) rate constants and on the positions of the equilibria between dormant and active states of initiator and polymer chain ends, respectively. The same considerations are true for other living processes involving dormant species, e.g., group transfer polymerization or controlled radical polymerization. Slow initiation of living carbocationic polymerization of isobutylen…

Protein Conformational Landscapes and Catalysis. Influence of Active Site Conformations in the Reaction Catalyzed by L-Lactate Dehydrogenase

2015

In the past decade, L-Lactate Dehydrogenase (LDH) has become an extremely useful marker in both clinical diagnosis and in monitoring the course of many human diseases. It has been assumed since the 1980s that the full catalytic process of LDH starts with the binding of the cofactor and the substrate followed by the enclosure of the active site by a mobile loop of the protein before the reaction takes place. In this paper, we show that the chemical step of the LDH-catalyzed reaction can proceed within the open loop conformation, and the different reactivity of the different protein conformations would be in agreement with the broad range of rate constants measured in single-molecule spectrom…