Thermodynamic studies in solution. Part IV. Solvent effect on the solvolysis of tert-butyl chloride. A new treatment of the experimental data

1979 ◽  
Vol 57 (5) ◽  
pp. 500-502 ◽  
Author(s):  
Joaquim Jose Moura Ramos ◽  
Jacques Reisse ◽  
M. H. Abraham
Keyword(s):  
Free Energy ◽  
Solvent Effect ◽  
Free Energies ◽  
Butyl Chloride ◽  
Activation Free Energy ◽  
Tert Butyl ◽  
New Treatment ◽  
The One ◽  
Activated Complex ◽  
Tert Butyl Chloride

A new treatment of the solvent effect on the solvolysis of tert-butyl chloride is proposed. This treatment is based on activation free energy measurements and on transfer free energy measurements of the reactant (R) on the one hand and of a model (M) of the activated complex (AC) on the other hand. Solute–solvent interaction free energies for the reactant, the activated complex and the model compound are estimated. This estimation involves the calculation of the free energy of cavity formation of these various solutes (R, AC, and M) in all the solvents. These cavity terms, which are a function of the cohesive properties of the solvent and of the surface of the cavity do not reflect the electronic structure of the solute whereas the interaction free energy term does. The method we propose can be described as a new 'experimental' approach for the study of the charge separation in an activated complex.

Orientational dependence of the translational energy transfer in the scattering of oriented fluoroform and tert‐butyl chloride molecules by a graphite(0001) surface

1990 ◽  
Vol 93 (10) ◽  
pp. 7416-7426 ◽  
Author(s):  
Stanislav I. Ionov ◽  
Michael E. LaVilla ◽  
Richard B. Bernstein
Keyword(s):  
Energy Transfer ◽  
Translational Energy ◽  
Butyl Chloride ◽  
Tert Butyl ◽  
Tert Butyl Chloride

Surface temperature dependence of the steric effect in the scattering of oriented tert‐butyl chloride and fluoroform molecules by graphite(0001)

1990 ◽  
Vol 93 (10) ◽  
pp. 7406-7415 ◽  
Author(s):  
Stanislav I. Ionov ◽  
Michael E. LaVilla ◽  
R. Scott Mackay ◽  
Richard B. Bernstein
Keyword(s):  
Surface Temperature ◽  
Temperature Dependence ◽  
Steric Effect ◽  
Butyl Chloride ◽  
Tert Butyl ◽  
Tert Butyl Chloride

scholarly journals tert-Butylation of 1-Naphthol with tert-Butyl Alcohol or tert-Butyl Chloride in the Presence of Sulfuric Acid or Zinc Chloride

1973 ◽  
Vol 31 (10) ◽  
pp. 831-834 ◽  
Author(s):  
Toshiyuki MIYATA ◽  
Takahiro HAMADA ◽  
Tsuneaki HIRASHIMA ◽  
Osamu MANABE ◽  
Hachiro HIYAMA
Keyword(s):  
Sulfuric Acid ◽  
Zinc Chloride ◽  
Butyl Alcohol ◽  
Butyl Chloride ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Tert Butyl Chloride

ChemInform Abstract: EVALUATION OF THE FORCE CONSTANT FOR THE CARBON-CHLORIDE STRETCHING VIBRATION FOR TERT-BUTYL CHLORIDE USING MINDO 3

1976 ◽  
Vol 7 (9) ◽  
pp. no-no
Author(s):  
DONALD G. GRACZYK ◽  
ROBERT L. JULIAN ◽  
JAMES W. TAYLOR ◽  
S. D. WORLEY
Keyword(s):  
Force Constant ◽  
Butyl Chloride ◽  
Tert Butyl ◽  
Stretching Vibration ◽  
Tert Butyl Chloride

Design and Thermodynamic Analysis on One-Step Amination of Benzene to Aniline Systems

2012 ◽  
Vol 550-553 ◽  
pp. 2607-2611
Author(s):  
Chun Hua Yang ◽  
Gang Chen ◽  
Long Zhang
Keyword(s):  
Hydrogen Peroxide ◽  
Free Energy ◽  
Equilibrium Constant ◽  
Gibbs Free Energy ◽  
Driving Force ◽  
Theoretical Basis ◽  
Free Energies ◽  
One Step ◽  
The One ◽  
Further Development

Seven systems of one-step synthesis of aniline were designed, and it was determined which one could occur spontaneously through the calculation of Gibbs free energy of it. Among the seven systems, the Gibbs free energy of the one with ammonia as the aminating agent and hydrogen peroxide as the oxidant was the lowest, thus its process driving force was the largest, that is, .For this system just mentioned above, the standard Gibbs free energies, the equilibrium constant and the equilibrium conversions of benzene under different conditions were discussed ,which was expected to provide a theoretical basis for further development and application of the system.

Article

1999 ◽  
Vol 77 (5-6) ◽  
pp. 934-942
Author(s):  
J Peter Guthrie
Keyword(s):  
Carbon Dioxide ◽  
Free Energy ◽  
Equilibrium Constants ◽  
Marcus Theory ◽  
Energy Of Activation ◽  
Free Energies ◽  
Orbital Theory ◽  
Activation Free Energy ◽  
Free Energy Of Activation ◽  
Rms Error

Rate constants for hydration of carbon dioxide and ketene can be calculated by applying No Barrier Theory, which needs only equilibrium constants and distortion energies, the latter calculated using molecular orbital theory. The calculated free energies of activation are in satisfactory agreement with experiment: the rms error in free energy of activation is 2.38 kcal/mol. These compounds can also be described using Marcus Theory or Multidimensional Marcus Theory using the transferable intrinsic barrier appropriate to simple carbonyl compounds; in this case the rms error in free energy of activation is 2.19 kcal/mol. The two methods agree on preferred mechanistic path except for uncatalyzed hydration of ketene where Multidimensional Marcus Theory leads to a lower activation free energy for addition to the C=O, while No Barrier Theory leads to a lower free energy of activation for addition to the C=CH2. A rate constant for hydroxide ion catalyzed hydration of ketene can be calculated and is in accord with preliminary experimental results.Key words: ketene, carbon dioxide, hydration, Marcus Theory, No Barrier Theory.

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