The trans–cis isomerisation of bis(dioxolene)bis(pyridine) ruthenium complexes

1992 ◽  
Vol 70 (6) ◽  
pp. 1849-1854 ◽  
Author(s):  
Yu-Hong Tse ◽  
Pamela R. Auburn ◽  
A. B. P. Lever
Keyword(s):  
Ruthenium Complexes ◽  
Activation Parameters ◽  
Visible Spectroscopy ◽  
Dissociative Mechanism ◽  
First Order ◽  
First Order Kinetics ◽  
Uv Visible ◽  
Considerable Range ◽  
Pyridine Concentration

The isomerisation of trans to cis bis(3,5-di-t-butylbenzosemiquinonato)bis(R-pyridine)ruthenium, Ru(R-Py)2(DTBDiox)2, is induced by warming with an excess of R-pyridine, where R = 3-chloro, 4-methyl, 4-phenyl, or 4-butyl. The rates of these reactions, for the species with R-Py = 3-chloropyridine, were monitored in o-dichlorobenzene by UV–visible spectroscopy against varying 3-chloropyridine and varying trans-[Ru(3-ClPy)2(DTBDiox)2] concentration. The data were found to obey first-order kinetics, −d[Ru(3-ClPy)2(DTBDiox)2/dt = kobsd[Ru(3-ClPy)2(DTBDiox)2], over a considerable range of pyridine concentration. A plot of 1/kobsd vs. [3-chloropyridine] is linear with a positive intercept. A dissociative mechanism is proposed for the isomerisation reaction. The activation parameters were determined for the specific case of R-Py = 3-chloropyridine. Electronic and electrochemical features of these species are briefly discussed.

The kinetics and the mechanism of oxidative decarboxylation of benzilic acid by acidic permanganate (stopped-flow technique) — An autocatalytic study

2004 ◽  
Vol 82 (9) ◽  
pp. 1372-1380 ◽  
Author(s):  
Sairabanu A Farokhi ◽  
Sharanappa T Nandibewoor
Keyword(s):  
Activation Parameters ◽  
Oxidative Decarboxylation ◽  
Two Stage ◽  
First Order ◽  
First Order Kinetics ◽  
Stage Process ◽  
Benzilic Acid ◽  
Reaction Constants ◽  
Kinetics Of ◽  
Good Agreement

The kinetics of the oxidation of benzilic acid by potassium permanganate in an acidic medium were studied spectrophotometrically. The reaction followed a two-stage process, wherein both stages of the reaction followed first-order kinetics with respect to permanganate ion and benzilic acid. The rate of the reaction increased with an increase in acid concentration. Autocatalysis was observed by one of the products, i.e., manganese(II). A composite mechanism involving autocatalysis has been proposed. The activation parameters of the reaction were calculated and discussed and the reaction constants involved in the mechanisms were calculated. There is a good agreement between the observed and calculated rate constants under different experimental conditions.Key words: oxidation, autocatalysis, benzilic acid, two-stage kinetics.

scholarly journals KINETICS OF REACTION BETWEEN MALACHITE GREEN AND HYDROXYL ION IN THE PRESENCE OF REDUCING SUGARS

2015 ◽  
Vol 23 (23) ◽  
pp. 61-72
Author(s):  
Dayo Felix Latona ◽  
Adewumi Oluwasogo Dada
Keyword(s):  
Malachite Green ◽  
Activation Parameters ◽  
Cell Compartment ◽  
First Order ◽  
Rate Determining Step ◽  
First Order Kinetics ◽  
Hydroxyl Ion ◽  
Kinetics Of Reaction ◽  
Kinetics Of ◽  
Sphere Mechanism

The reaction was studied via pseudo-first-order kinetics using a UV-1800 Shimadzu spectrophotometer with a thermostated cell compartment and interfaced with a computer. The reaction showed first order with respect to malachite green and sugar and hydroxyl ion concentrations. However, the reaction was independent of ionic strength and showed no dependence on the salt effect, indicating an inner sphere mechanism for the reaction. There was no polymerization of the reaction mixture with acrylonitrile, indicating the absence of radicals in the course of the reaction. Michaelis-Menten plot indicated the presence of a reaction intermediate in the rate-determining step. The activation parameters of the reaction have been calculated and products were elucidated by FTIR spectroscopy. The stoichiometry of the reaction is 1:1. A mechanism consistent with the above facts has been suggested.

scholarly journals Effect of heparin on thrombin inactivation by antithrombin-III

1978 ◽  
Vol 173 (3) ◽  
pp. 869-875 ◽  
Author(s):  
R Machovich ◽  
P Arányi
Keyword(s):  
Antithrombin Iii ◽  
Specific Activity ◽  
Activation Parameters ◽  
Heat Inactivation ◽  
Activation Entropy ◽  
First Order ◽  
Heparin Concentration ◽  
First Order Kinetics ◽  
Thermodynamic Activation Parameters ◽  
Time Courses

The inactivation of thrombin by heat and by its physiological inhibitor, antithrombin-III, shows quite different dependence on heparin concentration. Heparin at 250 microgram/ml protects thrombin against heat inactivation, and thrombin behaves heterogeneously in this reaction. In the absence of heparin, the thermodynamic activation parameters change with temperature (deltaH+ = 733 kJ/mol and 210 kJ/mol at 50 and 58 degrees C respectively). When heparin is present, heat inactivation of the protected thrombin species proceeds with deltaH+ = 88 kJ/mol and is independent of temperature in the same range. On the other hand, heparin at 0.125-2.5 microgram/ml accelerates the thrombin-antithrombin-III reaction. Thrombin does not show heterogeneity in this reaction and the time courses at any heparin concentration and any temperature between 0 and 37 degrees C appear to follow first-order kinetics. Activation enthalpy is independent of heparin concentration or temperature, deltaH+ = 82-101 kJ/mol, varying slightly with antithrombin-III concentration and thrombin specific activity. Heparin seems to exert its effect by increasing activation entropy. On the basis of these data we suggest a mechanism of action of heparin in the thrombin-antithrombin-III reaction which accounts for all the important features of the latter and seems to unify the different hypotheses that have been advanced.

Thermolysis of 5,5-dimethyl-4-aryl-Δ1-1,2,4-triazolin-3-ones in solution. Products, kinetics, substituent effects, and solvent effects

1981 ◽  
Vol 59 (1) ◽  
pp. 100-105 ◽  
Author(s):  
Lubomira M. Cabelkova-Taguchi ◽  
John Warkentin
Keyword(s):  
Transition State ◽  
Solvent Effects ◽  
Charge Separation ◽  
Substituent Effects ◽  
Activation Parameters ◽  
Oxidative Cyclization ◽  
First Order ◽  
Temperature Range ◽  
Aryl Amine ◽  
First Order Kinetics

A series of 5,5-dimethyl-4-aryl-Δ1-1,2,4-triazolin-3-ones (Ar = C6H5, p-C6H4CH3, p-C6H4OCH3, p-C6H4Cl, and p-C6H4Br) were prepared from the corresponding 4-arylsemicarbazones of acetone by oxidative cyclization on alumina. The triazolinones decompose in solution to N2, CO, and isopropylidene aryl amine, with first order kinetics, in the temperature range 148–200 °C. Average activation parameters are ΔH≠ = 35 kcal mol−1 and ΔS≠ = 8 cal K−1 mol−1. Substituent effects are correlated through σ-constants but the thermolyses are relatively insensitive to substituents, with ρ = −0.17 at 172.5 °C. Solvent effects indicate a transition state that is less polar than the ground state.It is tentatively concluded that the triazolinone fragmentation, like the analogous thermolysis of a Δ3-1,3,4-oxadiazolin-2-one, may be a fully-concerted but nonsynchronous process with a transition state involving little, if any, charge separation. Other mechanisms, except for those involving highly polar (e.g. zwitterionic) transition states, have not been ruled out.

scholarly journals Kinetics and Mechanism of Oxidation of Malic Acid by N-Bromonicotinamide (NBN) in the Presence of a Micellar System

2015 ◽  
Vol 52 ◽  
pp. 111-119
Author(s):  
L. Pushpalatha
Keyword(s):  
Malic Acid ◽  
Reaction Rate ◽  
Activation Parameters ◽  
Zero Order ◽  
Micellar System ◽  
First Order ◽  
First Order Kinetics ◽  
Rate Of Reaction ◽  
Different Temperatures ◽  
Experimental Findings

The oxidation of malic acid by N-bromonicotinamide in the presence of micellar system is studied. First order kinetics with respect to NBN is observed. The kinetics results indicate that the first order kinetics in hydroxy acid at lower concentrations tends towards a zero order at its higher concentrations. Inverse fractional order in [H+] and [nicotinamide] are noted throughout its tenfold variation. Variation of [Hg (OAc)2] and ionic strength of the medium do not bring about any significant change in the rate of reaction. Rate of the reaction increases with a decrease in the percentage of acetic acid. Decrease in the rate constant was observed with the increase in [SDS]. The values of rate constants observed at four different temperatures were utilized to calculate the activation parameters. A suitable mechanism consistent with the experimental findings has been proposed.

scholarly journals A kinetic study of Zn halide/TBAB-catalysed fixation of CO2 with styrene oxide in propylene carbonate

2019 ◽  
Vol 8 (1) ◽  
pp. 719-729 ◽  
Author(s):  
Abdul Rehman ◽  
M.F.M. Gunam Resul ◽  
Valentine C. Eze ◽  
Adam Harvey
Keyword(s):  
Propylene Carbonate ◽  
Styrene Oxide ◽  
Activation Parameters ◽  
Green Solvent ◽  
Acid Base ◽  
First Order ◽  
First Order Kinetics ◽  
Thermodynamic Activation Parameters ◽  
Styrene Carbonate ◽  
Comprehensive Study

Abstract Synthesis of styrene carbonate (SC) via the fixation of CO2 with styrene oxide (SO) has been investigated using a combination of zinc bromide (ZnBr2) and tetrabutylammonium halides (TBAX) as acid-base binary homogeneous catalysts. The combination of ZnBr2 and TBAB had a synergistic effect, which led to about 6-fold enhancement in the rate of SC formation as compared to using TBAB alone as a catalyst. Propylene carbonate (PC) was chosen as a green solvent for a comprehensive study of reaction kinetics. The reaction followed a first-order kinetics with respect to SO, CO2, and TBAB, whereas a fractional order was observed for the ZnBr2 when used in combination with the TBAB. Arrhenius and Eyring’s expressions were applied to determine the kinetic and thermodynamic activation parameters, where activation energy (Ea) of 23.3 kJ mol−1 was obtained for the SC formation over the temperature range of 90-120°C. The thermodynamic analysis showed that positive values for enthalpy (ΔH‡ = 18.53 kJ mol−1), Gibbs free energy (ΔG‡ = 79.74 kJ mol−1), whereas a negative entropy (ΔS‡ = –162.88 J mol−1 K−1) was obtained. These thermodynamic parameters suggest that endergonic and kinetically controlled reactions were involved in the formation of SC from SO and CO2.

scholarly journals Kinetics of Oxidation of Benzoin by N. Bromosuccinimide

2005 ◽  
Vol 4 (1) ◽  
pp. 55-61
Author(s):  
R. Sridharan ◽  
N. Mathiyalagan
Keyword(s):  
Dielectric Constant ◽  
Acetic Acid ◽  
Reaction Rate ◽  
Activation Parameters ◽  
Aqueous Acetic Acid ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
First Order Kinetics ◽  
Retarding Effect ◽  
Kinetics Of

Kinetics of Oxidation of Benzoin by N. Bromosuccinimide[NBS] 80% aqueous acetic acid has been investigated. The reaction follows first-order kinetics with respect to both[NBS] and [benzoin]. The effect of varying ionic strength and dielectric constant indicate the reaction is dipole-dipole type. Addition of succinimide(>NH), has a retarding effect on the rate of oxidation. The product of oxidation is benzil. By studying the effect of temparature on the reaction rate, the Arrhenius and the activation parameters have been calculated. A suitable mechanism has been proposed and a rate low explaining the experiment results is derived.

Solvent Effects on the Racemization of Optically Active Tris(N-substituted carbamodithioato)cobalt (III) Complexes

1979 ◽  
Vol 32 (8) ◽  
pp. 1653 ◽  
Author(s):  
LR Gahan ◽  
MJ O'Conner
Keyword(s):  
Carbon Tetrachloride ◽  
Solvent Effects ◽  
Reaction Mechanisms ◽  
Activation Parameters ◽  
Optically Active ◽  
Isokinetic Relationship ◽  
First Order ◽  
First Order Kinetics ◽  
Thermodynamic Activation Parameters ◽  
Wide Range

The thermal racemization in solution of some optically active tris(N-substituted carbamodithioato)- cobalt(III) complexes [N-substituents = diphenyl, dimethyl, diisopropyl, and tetramethylene (pyrrolidinyl)] has been measured polarimetrically in a range of solvents including dimethylformamide, acetonitrile, carbon tetrachloride, chlorobenzene, chloroform, toluene and ethanol. The metal-centred (Δ ↔ Λ) inversion reactions show first-order kinetics as expected for an intra- molecular process. Thermodynamic activation parameters for the reaction show that values of ΔS‡ occur over a wide range (from -124 to +60 J K-1 mol-1) as do the values of ΔH‡ (from 67�4 to 129�3 kJ mol-1). Values for ΔG‡ are reasonably constant. Although a similar mechanism for the metal-centred inversion is suggested for all compounds in the various solvents because of an observed isokinetic relationship between ΔH‡ and ΔS‡, with isokinetic temperatures in the range 312-369 K, it is clear that postulates of reaction mechanisms based on the value of ΔS‡ determined in only one solvent should be treated with caution. The optically active (-)546-tris(N,N-diisopropylcarbamodithioato)cobalt(III) complex photoracemizes in solution without decomposition. The rate of photoracemization is solvent-dependent being in the order bromoform � carbon tetrachloride ≈ chloroform �benzene.

Nitrogen Bridged Osmium-Ruthenium Complexes

1971 ◽  
Vol 49 (2) ◽  
pp. 207-210 ◽  
Author(s):  
Clive M. Elson ◽  
J. Gulens ◽  
John A. Page
Keyword(s):  
Absorption Band ◽  
Ruthenium Complexes ◽  
Second Order ◽  
Kcal Mole ◽  
First Order ◽  
First Order Kinetics ◽  
Equilibrium Concentrations

The formation of [(H2O)(NH3)4Ru—N2—Os(NH3)5]4+ by the reaction of cis-Ru(NH3)4(H2O)22+and Os(NH3)5N22+ has been studied over the range 15–45 °C. The reaction followed second order kinetics with kt = 1.2 × 10–1 M–1 s–1 at 25.0 °C and Ea = 16.8 ± 0.1 kcal/mole. Measurement of equilibrium concentrations gave Keq = 4 × 103 M−1 at 25.0 °C.The (4+) dimer was stable but removal of the excess cis-Ru(NH3)4(H2O)22+ reactant by oxidation at −0.10 V was followed by dimer decomposition. The breakup obeyed simple first order kinetics with kr = 2.9 × 10−5 s−1 at 25.0 °C.Oxidation of the (4+) dimer at + 0.10 V gave a stable (5+) dimer. Removal of the excess Os(NH3)5N22+ reactant at + 0.30 V was followed by decomposition of the (5+) dimer giving Os(NH3)5N22+ and RuIII(NH3)4X2. The decomposition again obeyed first order kinetics with k1 = 1.5 × 10−5 s−1 at 25.0 °C. The (5+) dimer has an intervalence–transfer absorption band at 755 nm and is characterized as [X(NH3)4RuIII—N2—OsII(NH3)5]5+.The studies were carried out in an aqueous H2SO4–K2SO4 electrolyte of pH 3.3, µ = 0.30.

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