First-order parallel and consecutive reaction mechanisms — Isosbestic points criterium

2008 ◽  
Vol 86 (9) ◽  
pp. 918-924 ◽  
Author(s):  
A E Croce
Keyword(s):  
Reaction Mechanism ◽  
Absorption Spectra ◽  
Rate Coefficients ◽  
Isosbestic Point ◽  
Experimental Conditions ◽  
Consecutive Reaction ◽  
Time Resolved ◽  
First Order ◽  
Kinetic Information ◽  
First Case

A criterium for the selection of reaction mechanism derived from a condition for isosbestic points occurrence is presented. Analytical relationships involving the molar absorption coefficients of the species, which participate in a mechanism of parallel first-order reactions and the corresponding rate coefficients, are also reported. A model system of four species that present overlapping absorption spectra may correspond to the reactant and products of a system of parallel or consecutive first-order reactions. In the first case, under experimental conditions in which the absorbances are additive, the presence of an isosbestic point in the spectrum of the reaction mixture at a given wavelength leads to a time-independent ratio of the degree of advancement of reaction variables. From this, relevant kinetic information may be extracted, namely, the ratio of the reaction rate coefficients. Moreover, the occurrence of isosbestic points allows discarding the second mechanism. This conclusion is independent of the number of absorbing species. Model calculated examples show the application of the equations here derived. The resolution for the general case of mechanisms of N first-order reactions is provided.Key words: chemical kinetics, time-resolved absorption spectra, reaction mechanism.

Antithrombin-mediated Inhibition of Factor Vlla-Tissue Factor Complex by the Synthetic Pentasaccharide Representing the Heparin Binding Site to Antithrombin

1996 ◽  
Vol 76 (01) ◽  
pp. 005-008 ◽  
Author(s):  
Jean Claude Lormeau ◽  
Jean Pascal Herault ◽  
Jean Marc Herbert
Keyword(s):  
Binding Site ◽  
Tissue Factor ◽  
Residual Activity ◽  
Coagulation Factors ◽  
Heparin Binding ◽  
Experimental Conditions ◽  
First Order ◽  
Heparin Binding Site ◽  
Coagulant Activity

SummaryWe examined the effect of the synthetic pentasaccharide representing the minimal binding site of heparin to antithrombin on the antithrombin-mediated inactivation of factor Vila bound to tissue factor. This effect was compared to the effect of unfractionated heparin. Using purified recombinant human coagulation factors and either a clotting or an amidolytic assay for the determination of the residual activity of factor Vila, we showed that the pentasaccharide was an efficient antithrombin-dependent inhibitor of the coagulant activity of tissue factor-factor Vila complex. In our experimental conditions, assuming a mean MW of 14,000 for heparin, the molar pseudo-first order rate constants for ATIII-mediated FVIIa inhibition by ATIII-binding heparin and by the synthetic pentasaccharide were found to be similar with respective values of 104,000 ± 10,500 min-1 and 112,000 ± 12,000 min-1 (mean ± s.e.m., n = 3)

Photocolouration of 2,4,4,6-Tetraaryl-4H-pyrans and Their Heteroanalogues: Importance of Hypervalent Photoisomers

1995 ◽  
Vol 60 (10) ◽  
pp. 1621-1633 ◽  
Author(s):  
Stanislav Böhm ◽  
Mojmír Adamec ◽  
Stanislav Nešpůrek ◽  
Josef Kuthan
Keyword(s):  
Reaction Kinetics ◽  
Absorption Spectra ◽  
Electronic Absorption ◽  
Electronic Absorption Spectra ◽  
Theoretical Data ◽  
Order Reaction ◽  
Bleaching Process ◽  
First Order ◽  
Photodegradation Products ◽  
Hypervalent Molecules

Molecular geometries of 2,4,4,6-tetraphenyl-4H-pyran (Ia), 4,4-(biphenyl-2,2e-diyl)-2,6-diphenyl-4H-pyran (Ib) and their heterocyclic isomers II-V were optimized by the PM3 method and used for the calculation of electronic absorption spectra by the CNDO/S-CI procedure. Comparison of the theoretical data with experimental UV-VIS absorption spectra made possible to select hypervalent molecules IIIa, IIIb, IVa and IVb being responsible for the photocolouration of 4H-pyrans Ia, Ib, while compounds Va, Vb, VI and VII come into account as possible photodegradation products. The bleaching process of the UV illuminated compound Ia is analyzed in terms of dispersive first-order reaction kinetics.

Determination of Complex Reaction Mechanisms

2006 ◽  
Author(s):  
John Ross ◽  
Igor Schreiber ◽  
Marcel O. Vlad
Keyword(s):  
Reaction Mechanism ◽  
Reaction Mechanisms ◽  
Reaction Pathway ◽  
Chemical Species ◽  
Rate Coefficients ◽  
Chemical System ◽  
Evolutionary Development ◽  
Complex Reaction ◽  
Oscillatory Reactions

In a chemical system with many chemical species several questions can be asked: what species react with other species: in what temporal order: and with what results? These questions have been asked for over one hundred years about simple and complex chemical systems, and the answers constitute the macroscopic reaction mechanism. In Determination of Complex Reaction Mechanisms authors John Ross, Igor Schreiber, and Marcel Vlad present several systematic approaches for obtaining information on the causal connectivity of chemical species, on correlations of chemical species, on the reaction pathway, and on the reaction mechanism. Basic pulse theory is demonstrated and tested in an experiment on glycolysis. In a second approach, measurements on time series of concentrations are used to construct correlation functions and a theory is developed which shows that from these functions information may be inferred on the reaction pathway, the reaction mechanism, and the centers of control in that mechanism. A third approach is based on application of genetic algorithm methods to the study of the evolutionary development of a reaction mechanism, to the attainment given goals in a mechanism, and to the determination of a reaction mechanism and rate coefficients by comparison with experiment. Responses of non-linear systems to pulses or other perturbations are analyzed, and mechanisms of oscillatory reactions are presented in detail. The concluding chapters give an introduction to bioinformatics and statistical methods for determining reaction mechanisms.

MODELLING NITROGEN PROCESSES IN SOIL: MATHEMATICAL DEVELOPMENT AND RELATIONSHIPS

1976 ◽  
Vol 56 (2) ◽  
pp. 71-78 ◽  
Author(s):  
D. R. CAMERON ◽  
C. G. KOWALENKO
Keyword(s):  
Time Dependent ◽  
Rate Coefficients ◽  
Nitrification Rate ◽  
Order Kinetic ◽  
Nitrogen Flow ◽  
First Order ◽  
Interaction Term ◽  
Flow Pathways ◽  
Adsorption Desorption ◽  
Temperature Water

A small subsystem model was developed to simulate the major nitrogen flow pathways in an unsaturated soil treated with ammonium sulphate. A nonlinear Freundlich equilibrium model and a Langmuir kinetic model were used to describe mathematically the adsorption–desorption of soluble NH4+ to the exchangeable and clay-fixed phases, respectively. Time dependent, microbial mediated first-order kinetic models were used to quantify the ammonification and nitrification processes. The subsystem model was then used as a research tool to derive ammonification and nitrification rate coefficients for a preceding incubation experiment conducted using different soil moisture contents and temperatures. The model yields reasonably good fits to the observed data. A subsequent regression analysis relating the coefficients to temperature and moisture pointed out the importance of the temperature–water content interaction term in quantifying microbial mediated processes.

The kinetics of hydration of tricalcium silicate

1970 ◽  
Vol 48 (21) ◽  
pp. 3291-3299 ◽  
Author(s):  
K. G. McCurdy ◽  
B. P. Erno
Keyword(s):  
Reaction Mechanism ◽  
Intermediate Product ◽  
Activation Energies ◽  
Tricalcium Silicate ◽  
Rate Data ◽  
Large Excess ◽  
First Order ◽  
Kinetics Of ◽  
Subsequent Decomposition

An investigation has been made of the kinetics of hydration of tricalcium silicate at several temperatures in a large excess of water in the presence of various added ions. The rate data have been interpreted by a reaction mechanism which involves: (a) the first order hydration of tricalcium silicate to form an intermediate product, 1.5CaO•SiO2, which can react by two pathways, (b) the direct first order decomposition of intermediate, 1.5CaO•SiO2, to form lime and silica or (b′) complexing of intermediate with silica and subsequent decomposition to form lime and silica. This reaction mechanism predicts the rate of production of base during the hydration. The effect of various added ions is interpreted in terms of the proposed mechanism.Rate constants and activation energies for the various steps in the proposed mechanism are reported.

The reaction of μ-oxo-bis(phthalocyaninato)iron(III) with hydrogen sulphide in the presence of pyridine: Evidence for axial coordination of dichloromethane

2005 ◽  
Vol 09 (03) ◽  
pp. 198-205 ◽  
Author(s):  
Fabrizio Monacelli ◽  
Elisa Viola
Keyword(s):  
Reaction Mechanism ◽  
Linear Function ◽  
Rate Constant ◽  
Hydrogen Sulphide ◽  
Stoichiometric Ratio ◽  
First Order ◽  
Axial Coordination ◽  
Elementary Sulphur ◽  
Increasing Function ◽  
Limiting Value

The oxo-bridged complex ( py ) FePc - O - FePc ( py ) ( py = pyridine , Pc = phthalocyaninato dianion) reacts in dichloromethane with hydrogen sulphide giving elementary sulphur and the reduced ( py )2( FePc ) complex in the stoichiometric ratio 1:1. Under excess py and H2S , the reaction is first-order and the rate constant at a given py concentration is an increasing function of the reducing agent concentration, with asymptotic tendency to a limiting value. This latter depends on the pyridine concentration being higher the lower is the base concentration. When the reaction is carried out in pure pyridine, the rate constant is, instead, a strictly linear function of [ H2S ], with zero intercept. A reaction mechanism is proposed where the dichloromethane is directly involved in the axial coordination about the iron centers and H2S competes efficiently with both pyridine and solvent.

Comparative measurements of annihilation rate coefficients of fluorine radicals in a r.f. SF6 plasma by different time-resolved actinometry techniques

1999 ◽  
Vol 116-119 ◽  
pp. 1123-1126
Author(s):  
V. Shogun ◽  
A. Tyablikov ◽  
V. Pashkov ◽  
W. Scharff ◽  
T. Wallendorf ◽  
...  
Keyword(s):  
Rate Coefficients ◽  
Annihilation Rate ◽  
Time Resolved
Sign in / Sign up

Export Citation Format

Share Document