Polymérisation du norbornène par des amorceurs au ruthénium. Etude cinétique de la réaction

1980 ◽  
Vol 58 (24) ◽  
pp. 2813-2818 ◽  
Author(s):  
Charles Tanielian ◽  
Alain Kiennemann ◽  
Temel Ösparpucu
Keyword(s):  
Kinetic Parameters ◽  
Homogeneous Catalysis ◽  
Reaction Mechanisms ◽  
Ligand Exchange ◽  
Alcohol Concentration ◽  
Zero Order ◽  
Slow Step ◽  
Variable Order ◽  
First Order ◽  
Initiation Step

The kinetic parameters for the polymerisation reaction of norbornene with RuCl3•3H2O, and RuCl2(PΦ3)3 using homogeneous catalysis have been determined (first-order with respect to two initiators, zero-order with respect to the monomer with RuCl3•3H2O, and variable order with RuCl2(PΦ3)3: Ea 6.2 kcal/mol for RuCl2(PΦ3)3 and 22.8 for RuCl3•3H2O) and leads us to propose different reaction mechanisms for the polymerisation starting from the two initiators, at least for the initiation step. With RuCl2(PΦ3)3 the slow step of the reaction is the metathesis whereas with RuCl3•3H2O the slow step is a ligand exchange at the initiator involving solvent (alcohol) by a dissociative or associative mechanism. This slow step is confirmed by a study of varying alcohol concentration and initiator aging. [Journal translation]

Coordination Compounds of Indium. Part XIX. Ligand Exchange Studies with Indium(III) Complexes of Trifluoromethyl-β-diketonates

1972 ◽  
Vol 50 (24) ◽  
pp. 3950-3957 ◽  
Author(s):  
Mrs. G. M. Tanner ◽  
D. G. Tuck ◽  
E. J. Wells
Keyword(s):  
Ligand Exchange ◽  
Coordination Compounds ◽  
Free Ligand ◽  
Intramolecular Proton Transfer ◽  
Zero Order ◽  
Monodentate Ligand ◽  
Ligand Exchange Reaction ◽  
First Order ◽  
Stereochemical Properties ◽  
Coalescence Temperature

The ligand exchange reaction between InL3 con plexes (L = CF3•CO•CH•CO•R− anion; R = methyl, i-butyl, phenyl, 2-naphthyl, and 2-thienyl) and excess free ligand (HL) has been studied in the solvents diisopropyl ketone, acetonitrile, benzene, and dimethylsulfoxide. Studies of the lifetimes of the reactants as obtained from their 19F n.m.r. line-widths show that the exchange is first order in InL3 concentration, but zero order in free ligand concentration. The coalescence temperature for the collapse of the n.m.r. 19F chemical shift between free and complexed ligand (~50 Hz) yields ΔG≠ for the exchange. The results are in agreement with the known stereochemical properties of indium(III) complexes. The rate-controlling process in the exchange is identified as the. rotation of one monodentate ligand about a partial double bond prior to intramolecular proton transfer to a second monodentate ligand.

Ligand exchange reactions of vanadium(III) β diketonate complexes

1978 ◽  
Vol 56 (7) ◽  
pp. 1012-1015 ◽  
Author(s):  
A. J. C. Nixon ◽  
D. R. Eaton
Keyword(s):  
Ligand Exchange ◽  
Zero Order ◽  
Second Order ◽  
Exchange Reactions ◽  
Rate Law ◽  
First Order ◽  
Kinetics Of ◽  
Incoming Ligand

The kinetics of ligand exchange reactions of V(III) β diketonates have been studied. The replacement of acetylacetone by hexafluoroacetylacetone involves a rate law with both first- and second-order terms in the incoming ligand. The replacement of acetylacetone by deuteroacetyl-acetone involves terms zero-order and first-order in the incoming ligand. Both reactions are markedly catalyzed by acids and inhibited by bases. A mechanism involving a dangling ligand intermediate is suggested. The rates of ligand exchange are much less than the rates of isomerization.

Evaluation of Kinetic Parameters at the Transport of Indole-3-acetic Acid Through Bulk Liquid Membranes

2017 ◽  
Vol 68 (5) ◽  
pp. 903-907
Author(s):  
Ecaterina Anca Serban ◽  
Ioana Diaconu ◽  
Elena Ruse ◽  
Georgiana Ileana Badea ◽  
Adriana Cuciureanu ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Kinetic Parameters ◽  
Trioctylphosphine Oxide ◽  
Bulk Liquid ◽  
Transport Parameters ◽  
Kinetics Parameters ◽  
First Order ◽  
Phase Concentration ◽  
Feed Phase ◽  
Indole 3 Acetic Acid

Indole-3-acetic acid is a growth phytohormone considered the most important representative of auxin class. This paper presents the assessment of some kinetic parameters in the process of transport of indole-3-acetic acid taking into consideration the kinetic model of consecutive irreversible first order reactions. It was pursued the influence upon the process of parameters such as: feed phase concentration, stripping phase concentration in the presence of two type carriers: tributyl phosphate (TBP) and trioctylphosphine oxide (TOPO). Depending on these transport parameters were calculated kinetics parameters such as: pseudo-first-order apparent membrane entrance and exit rate constants, the maximum flux at the entrance and exit out of the membrane. The highest values of the transport flux is obtained in the presence of carrier trioctylphosphine oxide (TOPO) at the concentration in the feed phase of 10-4 mol/L indole-3-acetic acid and a concentration of 10--2mol/L NaOH in the stripping phase.

Kinetics of catalytic reduction of nitrogen oxide by carbon monoxide on CuO/Al2O3 catalyst

1983 ◽  
Vol 48 (11) ◽  
pp. 3202-3208 ◽  
Author(s):  
Zdeněk Musil ◽  
Vladimír Pour
Keyword(s):  
Carbon Monoxide ◽  
Nitrogen Oxide ◽  
Rate Equation ◽  
Catalytic Reduction ◽  
Zero Order ◽  
Spectroscopic Measurements ◽  
First Order ◽  
Ir Spectroscopic ◽  
Kinetics Of ◽  
Al2o3 Catalyst

The kinetics of the reduction of nitrogen oxide by carbon monoxide on CuO/Al2O3 catalyst (8.36 mass % CuO) were determined at temperatures between 413 and 473 K. The reaction was found to be first order in NO and zero order in CO. The observed kinetics are consistent with a rate equation derived from a mechanism proposed on the basis of IR spectroscopic measurements.

Area-based speciation kinetic analysis of the multipollutant removal in Constructed Wetlands to enhance its treatment efficiency

2021 ◽  
Author(s):  
Manoj Kumar ◽  
Rajesh Singh
Keyword(s):  
Wastewater Treatment ◽  
Kinetic Analysis ◽  
Constructed Wetlands ◽  
Municipal Wastewater ◽  
Zero Order ◽  
Pollutant Removal ◽  
Municipal Wastewater Treatment ◽  
Treatment Efficiency ◽  
First Order ◽  
Present Study Area

In the present study area-based, pollutant removal kinetic analysis was considered using the Zero-order, first-order decay and efficiency loss (EL) models in the constructed wetlands (CWs) for municipal wastewater treatment....

Supercritical Fluid Deposition of Ruthenium Thin Films: A Kinetic Study

2007 ◽  
Vol 992 ◽  
Author(s):  
Christos F. Karanikas ◽  
James J. Watkins
Keyword(s):  
Thin Films ◽  
Growth Rate ◽  
Deposition Temperature ◽  
Zero Order ◽  
Measurable Effect ◽  
Deposition Rates ◽  
Reaction Pressure ◽  
Deposition Kinetics ◽  
First Order ◽  
Kinetics Of

AbstractThe kinetics of the deposition of ruthenium thin films from the hydrogen assisted reduction of bis(2,2,6,6-tetramethyl-3,5-heptanedionato)(1,5-cyclooctadiene)ruthenium(II), [Ru(tmhd)2cod], in supercritical carbon dioxide was studied in order to develop a rate expression for the growth rate as well as to determine a mechanism for the process. The deposition temperature was varied from 240°C to 280°C and the apparent activation energy was 45.3 kJ/mol. Deposition rates up to 30 nm/min were attained. The deposition rate dependence on precursor concentrations between 0 and 0.2 wt. % was studied at 260°C with excess hydrogen and revealed first order deposition kinetics with respect to precursor at concentrations lower then 0.06 wt. % and zero order dependence at concentrations above 0.06 wt. %. The effect of reaction pressure on the growth rate was studied at a constant reaction temperature of 260°C and pressures between 159 bar to 200 bar and found to have no measurable effect on the growth rate.

Consecutive reactions in the thermal decomposition of phenylalkyldiazirines

1977 ◽  
Vol 55 (20) ◽  
pp. 3596-3601 ◽  
Author(s):  
Michael T. H. Liu ◽  
Barry M. Jennings
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Parameters ◽  
Diazo Compounds ◽  
First Order ◽  
Temperature Range ◽  
Decomposition Reactions ◽  
Consecutive Reactions ◽  
Rate Processes ◽  
Subsequent Decomposition

The thermal decomposition of phenyl-n-butyldiazirine and of phenylmethyldiazirine in DMSO and in HOAc have been investigated over the temperature range 80–130 °C. The intermediate diazo compounds, 1-phenyl-1-diazopentane and 1-phenyldiazoethane respectively have been detected and isolated. The decomposition of phenyl-n-butyldiazirine and the subsequent decomposition of its product, 1-phenyl-1-diazopentane, are an illustration of consecutive reactions. The kinetic parameters for the isomerization and decomposition reactions have been determined. The isomerization of phenylmethyldiazirine to 1-phenyldiazoethane is first order and probably unimolecular but the kinetics for the subsequent reactions of 1-phenyldiazoethane are complicated by several competing rate processes.

Kinetics of bioactive compounds in functional spice Jiangpo during thermal processing

2012 ◽  
Vol 8 (3) ◽  
Author(s):  
Xiaoyan Dai ◽  
Chenhuan Yu ◽  
Qiaofeng Wu
Keyword(s):  
Kinetic Parameters ◽  
Bioactive Compounds ◽  
Thermal Processing ◽  
Order Rate Constant ◽  
Heat Processing ◽  
Order Kinetic ◽  
Time Intervals ◽  
First Order ◽  
Order Kinetic Model ◽  
Kinetics Of

Abstract Jiangpo is an increasingly popular East Asian spice which is made from Mangnolia officinalis bark and ginger juice. Since it induces bioactive compounds decomposition and has influence on final flavor and fragrance, cooking is regarded as the key operation in preparation of Jiangpo. To evaluate the bioactive compounds content changes of Jiangpo during thermal processing, kinetic parameters including reaction order, rate constant, T1/2 and activation energy of bioactive markers namely honokiol, magnolol and curcumin were determined. Cooking was set at temperatures 60, 90 and 120 °C for selected time intervals. Results displayed the thermal kinetic characteristics of the three compounds. Thermal degradation of Honokiol and magnolol both followed first order kinetic model and the loss of curcumin fitted second order. A mathematical model based on the obtained kinetic parameters has also been developed to predict the degradation of honokiol, magnolol and curcumin in non-isothermal state. All the information in this paper could contribute necessary information for optimizing the existing heat processing of Jiangpo.

scholarly journals N.M.R. studies of ligand exchange on acetylacetonatotrimethylplatinum(IV)

1975 ◽  
Vol 28 (4) ◽  
pp. 759 ◽  
Author(s):  
NS Ham ◽  
JR Hall ◽  
GA Swile
Keyword(s):  
Activation Energy ◽  
Quantitative Analysis ◽  
Ligand Exchange ◽  
Variable Temperature ◽  
Order Reaction ◽  
First Order Reaction ◽  
First Order ◽  
Cdcl3 Solution ◽  
Made In

A quantitative analysis of the variable-temperature 1H N.M.R. spectra of acetylacetonatotrimethyl-platinum(IV) has been made. In CDCl3 solution the exchange of acetylacetonate ligands is a first-order reaction and proceeds predominantly by dissociation of the dimer into two separated five-coordinate activated complexes. The activation energy is 61.5 � 0.8 kJ mol-1.

A Stable Mixed Element Method for the Biharmonic Equation with First-Order Function Spaces

2017 ◽  
Vol 17 (4) ◽  
pp. 601-616 ◽  
Author(s):  
Zheng Li ◽  
Shuo Zhang
Keyword(s):  
Biharmonic Equation ◽  
Two Dimensions ◽  
Zero Order ◽  
Helmholtz Decomposition ◽  
Numerical Verification ◽  
Order Function ◽  
First Order ◽  
Mixed Element ◽  
New Formulation ◽  
Element Method

AbstractThis paper studies the mixed element method for the boundary value problem of the biharmonic equation {\Delta^{2}u=f} in two dimensions. We start from a {u\sim\nabla u\sim\nabla^{2}u\sim\operatorname{div}\nabla^{2}u} formulation that is discussed in [4] and construct its stability on {H^{1}_{0}(\Omega)\times\tilde{H}^{1}_{0}(\Omega)\times\bar{L}_{\mathrm{sym}}^% {2}(\Omega)\times H^{-1}(\operatorname{div},\Omega)}. Then we utilise the Helmholtz decomposition of {H^{-1}(\operatorname{div},\Omega)} and construct a new formulation stable on first-order and zero-order Sobolev spaces. Finite element discretisations are then given with respect to the new formulation, and both theoretical analysis and numerical verification are given.

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