Calculating initial-state-selected reaction probabilities from thermal flux eigenstates: A transition-state-based approach

2005 ◽  
Vol 123 (20) ◽  
pp. 204114 ◽  
Author(s):  
Fermín Huarte-Larrañaga ◽  
Uwe Manthe
Keyword(s):  
Transition State ◽  
Thermal Flux ◽  
Initial State

Solvolysis of isopropyl bromide in ethanol–water mixtures. Dissection into initial state and transition state contributions

1976 ◽  
Vol 54 (24) ◽  
pp. 3944-3948 ◽  
Author(s):  
Wiendelt Drenth ◽  
Michael Cocivera
Keyword(s):  
Vapor Pressure ◽  
Transition State ◽  
Thermodynamic Parameters ◽  
Activation Parameters ◽  
Solvent Composition ◽  
Initial State ◽  
Partial Vapor Pressure ◽  
State Variation

Rates were determined for the solvolysis of isopropyl bromide in ethanol–water mixtures (20 to 80% by volume of ethanol) at 50 and 75 °C and the corresponding activation parameters calculated. From the partial vapor pressure of isopropyl bromide over the various solutions at 50 and 75 °C, the variations in its initial state thermodynamic parameters were calculated. Thus, the variation in the activation parameters with solvent composition could be analyzed in terms of initial and transition state contributions. The initial state variation dominates according to a unimolecular as well as to a bimolecular treatment of data.

Solvent effect on the initial state and transition state of anation of pentaammine-aquachromium(III) ion by thiocyanate

1993 ◽  
Vol 18 (1) ◽  
pp. 110-112 ◽  
Author(s):  
Olga A. ◽  
J�n Benko ◽  
Ol'ga Voll�rov� ◽  
Vladislav Holba
Keyword(s):  
Transition State ◽  
Solvent Effect ◽  
Initial State

Initial state and transition state contributions to solvent effects on activation enthalpies for substitution reactions of tris(1,10-phenanthroline)iron(II) in aqueous methanol

1983 ◽  
Vol 8 (3) ◽  
pp. 148-152 ◽  
Author(s):  
Michael J. Blandamer ◽  
John Burgess ◽  
Timothy Digman ◽  
Philip P. Duce ◽  
John P. McCann ◽  
...  
Keyword(s):  
Transition State ◽  
Solvent Effects ◽  
Aqueous Methanol ◽  
Substitution Reactions ◽  
Initial State

Secondary Kinetic Isotope Effects in Bimolecular Nucleophilic Substitutions. V. The Role of the Solvent in the Reaction Between Methyl Iodide and Pyridine

1972 ◽  
Vol 50 (7) ◽  
pp. 982-985 ◽  
Author(s):  
K. T. Leffek ◽  
A. F. Matheson
Keyword(s):  
Transition State ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
State Structure ◽  
Transition State Structure ◽  
Initial State ◽  
Nucleophilic Substitutions ◽  
Kinetic Isotope ◽  
Deuterium Isotope Effects

Secondary kinetic deuterium isotope effects are presented for the reaction of methyl-d3 iodide and pyridine in four different solvents. Calculations on mass and moment of inertia change with deuteration in the initial state and an assumed tetrahedral transition state, together with internal rotational effects, are used to rationalize the inverse isotope effects. It is concluded from the variation of the isotopic rate ratio, that the transition state structure varies with solvent.

scholarly journals Application of Singh-Jha Equation in the Evaluation of b* Parameter of Laidler-Landskroener Equation in the Hydrolysis of Vinyl Acetate

2010 ◽  
Vol 7 (4) ◽  
pp. 1170-1173
Author(s):  
Sangita Sharma ◽  
Bijal Vyas ◽  
Falguni Thakkar ◽  
Ketan Patel ◽  
J. J. Vora
Keyword(s):  
Organic Solvent ◽  
Transition State ◽  
Vinyl Acetate ◽  
Alkaline Hydrolysis ◽  
Initial State ◽  
Closed Approach ◽  
Rate Of Hydrolysis ◽  
Solvent Molecules ◽  
Hydrolysis Of

Singh-Jha method is applied to calculate b* of Laidler-Landskroener equation, the distance of closed approach of solvent molecules to the activated complexes in alkaline hydrolysis of vinyl acetate. This method is applied to alkaline hydrolysis of vinyl acetate in water enriched ethanol between 30 °C and 35 °C. The rate of hydrolysis decreases with the increase of content of organic solvent at both temperatures. The size of transition state was found to be large as compared to the initial state. The b* was found to be 3.7693Å which is in agreement with the values obtained earlier.

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