scholarly journals Effect of excess free energy of solvents on the oxidation of methionine by quinolinium fluorochromate: A kinetic study

2008 ◽  
Vol 73 (7) ◽  
pp. 735-744 ◽  
Author(s):  
D.S. Bhuvaneshwari ◽  
K.P. Elango
Keyword(s):  
Free Energy ◽  
Excess Free Energy ◽  
Activation Parameters ◽  
Chloroacetic Acid ◽  
Reaction Rates ◽  
Solvent Mixtures ◽  
Free Energy Function ◽  
Different Temperatures ◽  
Oxidation Of Methionine ◽  
Quinolinium Fluorochromate

The oxidation of methionine by quinolinium fluorochromate (QFC) was studied in the presence of chloroacetic acid, in water/organic solvent mixtures of varying excess molar free energy function. The reaction is first order with respect to both QFC and acid. The reaction rates were determined at different temperatures and the activation parameters computed. The rate data was correlated with different solvent parameters using linear multiple regression analysis. From the results, information on the solvent-reactants and the solvent-transition state interactions was obtained. .

scholarly journals Solvation model for the oxidation of methionine by imidazolium fluorochromate in aqueous acetic acid medium

2006 ◽  
Vol 71 (1) ◽  
pp. 19-25 ◽  
Author(s):  
John Bincy ◽  
M. Pandeeswaran ◽  
D.S. Bhuvaneshwari ◽  
K.P. Elango
Keyword(s):  
Acetic Acid ◽  
Activation Parameters ◽  
Chloroacetic Acid ◽  
Reaction Rates ◽  
Aqueous Acetic Acid ◽  
Solvation Model ◽  
Acetic Acid Medium ◽  
Different Temperatures ◽  
Solute Interactions ◽  
Oxidation Of Methionine

The oxidation of methionine by imidazolium fluorochromate (IFC) were studied, in the presence of chloroacetic acid, in water-acetic acid mixtures of varying molar compositions. The reaction is first order with respect to methionine, IFC and acid. The reaction rates were determined at different temperatures and the activation parameters were computed. The reaction rate increases with increasing mole fraction of acetic acid in the mixture and specific solvent-solvent-solute interactions were found to predominate (86 %). A solvation model and a probable mechanism for the reaction are postulated.

scholarly journals Kinetics and mechanism of the oxidation of methionine by quinolinium chlorochromate

2005 ◽  
Vol 70 (2) ◽  
pp. 145-151 ◽  
Author(s):  
M. Pandeeswaran ◽  
John Bincy ◽  
D.S. Bhuvaneshwari ◽  
K.P. Elango
Keyword(s):  
Acetic Acid ◽  
Reaction Rate ◽  
Activation Parameters ◽  
Chloroacetic Acid ◽  
Reaction Rates ◽  
Solvation Model ◽  
First Order ◽  
Different Temperatures ◽  
Solute Interactions ◽  
Oxidation Of Methionine

The oxidation of methionine by quinolinium chlorochromate (QCC) has been studied, in the presence of chloroacetic acid, and in water-acetic acid mixtures of varying mole fractions. The reaction is first order with respect to methionine, QCC and acid. The reaction rates were determined at three different temperatures (25, 35 and 45 ?C) and the activation parameters were computed. The reaction rate increased with increasing mole fraction of acetic acid in the mixture and specific solvent-solvent-solute interactions were found to predominate (81 %). A solvation model and a suitable mechanism for the reaction are postulated.

scholarly journals Oxidation of Methionine by Tripropylammonium Fluorochromate-A Kinetic and Mechanistic Study

2011 ◽  
Vol 8 (2) ◽  
pp. 643-648 ◽  
Author(s):  
S. Sheik Mansoor
Keyword(s):  
Acetic Acid ◽  
Activation Parameters ◽  
Chloroacetic Acid ◽  
Mechanistic Study ◽  
Aqueous Acetic Acid ◽  
Acetic Acid Medium ◽  
Different Temperatures ◽  
Aqueous Mixture ◽  
Oxidation Of Methionine ◽  
Kinetics Of

The kinetics of oxidation of methionine (Met) by tripropylammonium fluorochromate (TriPAFC) has been studied in the presence of chloroacetic acid in aqueous acetic acid medium. The reaction is first order with respect to methionine, TriPAFC and acid. The reaction rate has been determined at different temperatures and activation parameters calculated. With an increase in the amount of acetic acid in its aqueous mixture, the rate increases. The reaction does not induce polymerization of acrylonitrile. A suitable mechanism has been proposed.

Kinetics of Ion-Pair Effect of Aquation of Bromopentaammine Cobalt(III) Complex in Different Dicarboxylate Media

2011 ◽  
Vol 324 ◽  
pp. 166-169 ◽  
Author(s):  
Farah Zeitouni ◽  
Gehan El-Subruiti ◽  
Ghassan Younes ◽  
Mohammad Amira
Keyword(s):  
Free Energy ◽  
Solvent Effect ◽  
Compensation Effect ◽  
Ion Pairing ◽  
Reaction Rates ◽  
Ion Pair ◽  
Free Energy Of Activation ◽  
Different Types ◽  
Different Temperatures ◽  
Kinetics Of

The rate of aquation of bromopentaammine cobalt(III) ion in the presence of different types of dicarboxylate solutions containing tert-butanol (40% V/V) have been measured spectrophotometrically at different temperatures (30-600°C) in the light of the effects of ion-pairing on reaction rates and mechanism. The thermodynamic and extrathermodynamic parameters of activation have been calculated and discussed in terms of solvent effect on the ion-pair aquation reaction. The free energy of activation ∆Gip* is more or less linearly varied among the studied dicarboxylate ion-pairing ligands indicating the presence of compensation effect between ∆Hip* and ∆Sip*. Comparing the kip values with respect of different buffers at 40% of ter-butanol is introduced.

scholarly journals Reactivity of Phenol and Aniline towards Quinolinium Chloro Chromate: A Comparative Oxidation Kinetic Study

2015 ◽  
Vol 59 ◽  
pp. 81-92
Author(s):  
Seplapatty Kalimuthu Periyasamy ◽  
H. Satham Hussain ◽  
R. Manikandan
Keyword(s):  
Oxidation Kinetic ◽  
Activation Parameters ◽  
Dipole Interaction ◽  
Reaction Rates ◽  
Hydrogen Ion ◽  
Aqueous Acetic Acid ◽  
Acetic Acid Medium ◽  
First Order ◽  
Different Temperatures ◽  
Kinetics Of

The kinetics of Oxidation of Phenol and aniline by quinolinium Chlorochromate (QCC) in aqueous acetic acid medium leads to the formation of quinone and azobenzene respectively. The reactions are first order with respect to both Phenol and aniline. The reaction is first order with respect to quinolinium chlorochromate (QCC) and is catalyzed by hydrogen ion. The hydrogen-ion dependence has the form: kobs = a+b [H+]. The rate of oxidation decreases with increasing dielectric constant of solvent, indicating the presence of an ion-dipole interaction. The reaction does not induced the polymerization of acrylonitrile. The retardation of the rate by the addition of Mn2+ ions confirms that a two electron transfer process is involved in the reaction. The reaction rates have been determined at different temperatures and the activation parameters have been calculated. From the above observations kinetic results a probable mechanism have been proposed.

Temperature, Dynamics, and Enzyme-Catalyzed Reaction Rates

2020 ◽  
Vol 49 (1) ◽  
pp. 163-180 ◽  
Author(s):  
Vickery L. Arcus ◽  
Adrian J. Mulholland
Keyword(s):  
Molecular Mechanisms ◽  
Activation Parameters ◽  
Reaction Rates ◽  
Rate Theory ◽  
Different Temperatures ◽  
State Ensemble ◽  
Catalyzed Reactions ◽  
Enzyme Catalyzed Reactions ◽  
Transition State Ensemble ◽  
Rate Limiting

We review the adaptations of enzyme activity to different temperatures. Psychrophilic (cold-adapted) enzymes show significantly different activation parameters (lower activation enthalpies and entropies) from their mesophilic counterparts. Furthermore, there is increasing evidence that the temperature dependence of many enzyme-catalyzed reactions is more complex than is widely believed. Many enzymes show curvature in plots of activity versus temperature that is not accounted for by denaturation or unfolding. This is explained by macromolecular rate theory: A negative activation heat capacity for the rate-limiting chemical step leads directly to predictions of temperature optima; both entropy and enthalpy are temperature dependent. Fluctuations in the transition state ensemble are reduced compared to the ground state. We show how investigations combining experiment with molecular simulation are revealing fundamental details of enzyme thermoadaptation that are relevant for understanding aspects of enzyme evolution. Simulations can calculate relevant thermodynamic properties (such as activation enthalpies, entropies, and heat capacities) and reveal the molecular mechanisms underlying experimentally observed behavior.

scholarly journals Theoretical investigations on temperature dependence of thermodynamic properties and concentration fluctuations of In-Tl binary liquid alloys by optimization method

BIBECHANA ◽  
2017 ◽  
Vol 15 ◽  
pp. 11-23
Author(s):  
G K Shrestha ◽  
I S Jha ◽  
B K Singh
Keyword(s):  
Free Energy ◽  
Liquid Alloy ◽  
Entire Range ◽  
Excess Free Energy ◽  
Concentration Fluctuations ◽  
Binary Liquid ◽  
Energy Of Mixing ◽  
Different Temperatures ◽  
Free Energy Of Mixing ◽  
Best Fit

The thermodynamic properties, i.e. free energy of mixing (GM), heat of mixing (HM), entropy of mixing (SM) and activity (ai) of the component i (i , and structural property i.e. concentration fluctuations in long wave-length limit [Scc(0)] of In-Tl binary liquid alloy at a specified temperature have been investigated in the framework of quasi-lattice model on assuming the coupled effect of size ratio and entropic (or energetic) as well as enthalpic effect. These properties of In-Tl liquid alloy at 723 K have been computed theoretically by estimating the best fit value of order energy parameter (W) and size ratio () over the entire range of concentration in order to match their experimental values. The best fit value of  W at 723 K has been used to determine the values of W at different temperatures with the help of temperature derivative of W which are then used for the optimization procedure in order to calculate the corresponding values of excess free energy of mixing, partial excess free energy of mixing and activity of the components involved in the alloy at different temperatures. These parameters have been used to investigate the concentration fluctuations in long wavelength limit {Scc(0)} of In-Tl binary liquid alloy at different temperatures over the entire range of concentration which have been used to predict the various other structural properties like excess stability function (EXS), diffusion coefficient ratio (Dm/Did), short range order parameter (α1) at different temperatures.BIBECHANA 15 (2018) 11-23

scholarly journals Extracting the Grain Boundary Character/Free Energy Relationship from the Microstructure: Pure and Tilt Boundaries

1997 ◽  
Vol 472 ◽  
Author(s):  
B. Adams ◽  
D. Kinderlehrer ◽  
S. Ta'asan ◽  
W.W. Mullins ◽  
S. Costiner
Keyword(s):  
Free Energy ◽  
Grain Boundary ◽  
Excess Free Energy ◽  
Free Energy Function ◽  
Triple Junctions ◽  
Grain Boundary Character ◽  
Classical Work ◽  
Tilt Boundaries ◽  
Lattice Misorientation ◽  
Two Parameter

ABSTRACTAnalysis is described to extract the excess free energy of grain boundaries from the mesotexture of well-equilibrated polycrystalline samples. The approach is based upon the force and torque balances at triple junctions described in the classical work of Herring [1]. The main advantage of the approach is that the free energy function is obtained over the full fundamental zone of grain boundary types. For the purposes of exposition, the method is described for specified two-parameter hypersurfaces in the fundamental zone for cubic polycrystals (the sets of pure <100> and <111> tilt boundaries) and the free energy is assumed to depend only upon the lattice misorientation. Results from testbed simulations are presented.

Kinetic and Mechanistic Aspects of Osmium(VIII) Catalyzed Oxidation of DL-ornithine by Copper(III) Periodate Complex in Aqueous Alkaline Medium

2010 ◽  
Vol 224 (06) ◽  
pp. 865-882 ◽  
Author(s):  
Jyothi C. Abbar ◽  
Shweta J. Malode ◽  
Sharanappa T. Nandibewoor
Keyword(s):  
Alkaline Medium ◽  
Activation Parameters ◽  
Reaction Rates ◽  
Oxidation Products ◽  
Slow Step ◽  
Thermodynamic Quantities ◽  
Aqueous Alkaline Medium ◽  
Uncatalyzed Reaction ◽  
Different Temperatures ◽  
Reaction Constants

AbstractThe oxidation of DL-ornithine monohydrochloride (OMH) by diperiodatocuprate(III) (DPC) has been investigated in the presence of osmium(VIII) catalyst in aqueous alkaline medium at a constant ionic strength of 0.20 mol dm−3 spectrophotometrically. The reaction exhibits 1:4 stoichiometry i.e., [OMH]: [DPC]. The order of the reaction with respect to [DPC] was unity while the order with respect to [OMH] was less than unity over the concentration range studied. The rate increased with an increase in [OH –] and decreased with an increase in [IO4−]. The order with respect to [Os(VIII)] was unity. The reaction rates revealed that Os(VIII) catalyzed reaction was about nine-fold faster than the uncatalyzed reaction. The oxidation products were identified by spectral analysis. Suitable mechanism has been proposed. The reaction constants involved in the different steps of the reaction mechanism were calculated. The catalytic constant (KC) was also calculated at different temperatures. The activation parameters with respect to slow step of the mechanism and also the thermodynamic quantities were determined. Kinetic experiments suggest that [OsO4(OH)2]2− is the reactive Os(VIII) species and [Cu(H2IO6)(H2O)2] is the reactive copper(III) species.

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