Solvent effects on the activation parameters of the reaction between an α-tocopherol analogue and dpph•: The role of H-bonded complexes

2012 ◽  
Vol 44 (8) ◽  
pp. 524-531 ◽  
Author(s):  
Mario C. Foti
Keyword(s):  
Solvent Effects ◽  
Activation Parameters ◽  
Bonded Complexes

Can the Lewis basicity of an isolated solvent molecule be used for characterizing solvent effects?

2020 ◽  
Vol 16 ◽  
Author(s):  
Jean-François Gal ◽  
Pierre-Charles Maria
Keyword(s):  
Solvent Effects ◽  
Molecular Level ◽  
Solvent Molecule ◽  
Lewis Base ◽  
Bulk Liquid ◽  
Donor Number ◽  
Special Focus ◽  
Solution Processes ◽  
Inert Solvent

Background: The ubiquitous Lewis acid/base interactions are important in solution processes. Analytical chemistry may benefit of a better understanding of the role of Lewis basicity, at the molecular level or acting through a bulk solvent effect. Objective: To clearly delineate (i) the basicity at a molecular level, hereafter referred as solute basicity, and (ii) the solvent basicity, which is a bulk-liquid property. Method: The literature that relates Lewis basicity scales and solvent effects is analyzed. A special focus is placed on two extensive scales, the Donor Number, DN, and the BF3 affinity scale, BF3A, which were obtained by calorimetric measurement on molecules as solutes diluted in a quasi-inert solvent, and therefore define a molecular Lewis basicity. We discuss the validity of these solute scales when regarded as solvent scales, in particular when the basicity of strongly associated liquids is discussed. Results: We demonstrate the drawbacks of confusing the Lewis basicity of a solvent molecule, isolated as solute, and that of the bulk liquid solvent itself. Conclusion: Consequently, we recommend a reasoned use of the concept of Lewis basicity taking clearly into account the specificity of the process for which a Lewis basicity effect may be invoked. In particular, the action of the Lewis base, either as an isolated entity, or as a bulk liquid, must be distinguished.

Thermodynamic and Kinetic Investigation of the Solvent Effect on the Oxidation of [Co(en)2SCH2COO]+ with S2O82- In Water-Methanol and Water-tert-Butyl Alcohol Mixtures

1993 ◽  
Vol 58 (5) ◽  
pp. 1001-1006 ◽  
Author(s):  
Oľga Vollárová ◽  
Ján Benko
Keyword(s):  
Transfer Functions ◽  
Activation Parameters ◽  
Butyl Alcohol ◽  
Oxidation Of Co ◽  
Kinetics Of Oxidation ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Alcohol Mixtures ◽  
Kinetics Of

The kinetics of oxidation of [Co(en)2SCH2COO]+ with S2O82- was studied in water-methanol and water-tert-butyl alcohol mixtures. Changes in the reaction activation parameters ∆H≠ and ∆S≠ with varying concentration of the co-solvent depend on the kind of the latter, which points to a significant role of salvation effects. The solvation effect on the reaction is discussed based on a comparison of the transfer functions ∆Ht0, ∆St0 and ∆Gt0 for the initial and transition states with the changes in the activation parameters accompanying changes in the CO-solvent concentration. The transfer enthalpies of the reactant were obtained from calorimetric measurements.

scholarly journals Solvent Effects and Activation Parameters for the Isotopic Exchange Reaction between Lithium Bromide and Butyl Bromide in Acetone--Water Mixtures.

1977 ◽  
Vol 31a ◽  
pp. 539-546 ◽  
Author(s):  
Allan Holmgren ◽  
C. J. Ballhausen ◽  
K. Schaumburg ◽  
H. Svanholt ◽  
Paul Hagenmuller ◽  
...  
Keyword(s):  
Exchange Reaction ◽  
Solvent Effects ◽  
Isotopic Exchange ◽  
Lithium Bromide ◽  
Activation Parameters ◽  
Butyl Bromide ◽  
Isotopic Exchange Reaction ◽  
Acetone Water

scholarly journals DFT investigation of role of N – H⋯O and N – H⋯π interactions in the stabilization of the hydrogen bonded complexes of anisole with aromatic amines

Heliyon ◽  
2019 ◽  
Vol 5 (7) ◽  
pp. e02155 ◽  
Author(s):  
Anil Singh Rajpurohit ◽  
R. Rajesh ◽  
R. Raj Muhamed ◽  
M. Jaccob ◽  
A. Justin Adaikala Baskar ◽  
...  
Keyword(s):  
Aromatic Amines ◽  
Π Interactions ◽  
Bonded Complexes ◽  
Hydrogen Bonded

scholarly journals Role of vibrational anharmonicity in atmospheric radical hydrogen-bonded complexes

2009 ◽  
Vol 11 (30) ◽  
pp. 6377 ◽  
Author(s):  
M. Torrent-Sucarrat ◽  
J. M. Anglada ◽  
J. M. Luis
Keyword(s):  
Vibrational Anharmonicity ◽  
Bonded Complexes ◽  
Hydrogen Bonded

The Role of π Electrons in the Formation of Benzene-Containing Lithium-Bonded Complexes

ChemPhysChem ◽  
2011 ◽  
Vol 12 (18) ◽  
pp. 3584-3590 ◽  
Author(s):  
Yanli Zeng ◽  
Min Zhu ◽  
Lingpeng Meng ◽  
Shijun Zheng
Keyword(s):  
Bonded Complexes

Solvent Effects in Carbohydrate Binding by Synthetic Receptors: Implications for the Role of Water in Natural Carbohydrate Recognition

2008 ◽  
Vol 120 (14) ◽  
pp. 2733-2736 ◽  
Author(s):  
Emmanuel Klein ◽  
Yann Ferrand ◽  
Nicholas P. Barwell ◽  
Anthony P. Davis
Keyword(s):  
Solvent Effects ◽  
Carbohydrate Binding ◽  
Synthetic Receptors ◽  
Carbohydrate Recognition
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