SULPHONIUM SALT SOLVOLYSIS: PART IV. SOLVENT EFFECTS

1963 ◽  
Vol 41 (7) ◽  
pp. 1679-1685 ◽  
Author(s):  
J. B. Hyne ◽  
J. H. Jensen
Keyword(s):  
Dielectric Constant ◽  
Ethylene Glycol ◽  
Binary Mixtures ◽  
Solvent Effects ◽  
Solvent Composition ◽  
Activation Process

The variation of rate of solvolysis of dimethyl-t-butyl sulphonium iodide as a function of solvent composition is reported for various binary mixtures of water with ethanol, N,N-dimethylformamide, N-methylformamide, dioxane, and ethylene glycol. The inadequacy of solvent bulk dielectric constant as a correlating parameter is demonstrated and solvent Y and Z parameters are compared in this respect. The importance of the specific microscopic role of the solvent in the activation process is demonstrated and a possible important nucleophilic role for the amides suggested. Deviations in dioxane and ethylene glycol systems are discussed.

The Solvent Effects on Kinetics and Mechanism of Zinc or Cadmium Halide Catalyzed Reactions of Hydrosilanes with Hydroxylic Reagents

2004 ◽  
Vol 69 (12) ◽  
pp. 2281-2296 ◽  
Author(s):  
Jerzy J. Chruściel
Keyword(s):  
Dielectric Constant ◽  
Solvent Effects ◽  
Kinetic Method ◽  
Kinetic Studies ◽  
Reaction Rates ◽  
Nucleophilic Catalysis ◽  
Effect Of Solvent ◽  
Cadmium Bromide ◽  
Catalyzed Reactions

The effect of solvent composition on reaction rates was studied by a kinetic method for reactions of Et3SiH with Ph2Si(OH)2 in the presence of ZnCl2 in a mixture of DMF and THF or Et3SiH with PhCOOH and cadmium bromide CdBr2 in DMF-1,4-dioxane and DMF-THF. A decrease in reaction rates with decreasing polarity of the medium (and its dielectric constant) has been observed. The kinetic order of dehydrocoupling reaction with respect to DMF was determined from kinetic studies. The constants of nucleophilic catalysis with DMF (λ) were found. The role of DMF in the mechanism of dehydrocoupling of hydrosilanes with hydroxylic reagents in the presence of ZnX2 and CdX2 halides (X = Cl, Br, I) is discussed.

Solvent Effects on the Kinetics and Mechanism of the Acid-Catalysed Hydrolysis of Diterf.-butylsuccinate in Dioxane-Water Mixtures

1985 ◽  
Vol 40 (1) ◽  
pp. 84-91 ◽  
Author(s):  
Adel N. Asaad ◽  
Fayez Y. Khalil
Keyword(s):  
Dielectric Constant ◽  
Solvent Effects ◽  
Rate Constants ◽  
Mixed Type ◽  
Reaction Rate ◽  
Solvent Composition ◽  
Water Molecules ◽  
Molecular Dipole ◽  
First Order ◽  
Hydrolysis Of

The acid-catalysed hydrolysis of ditert.-butylsuccinate in dioxane-water mixtures proceeds via consecutive first-order reactions. The rate constants kI and kII corresponding to the two steps decrease with increasing dioxane content of the medium. After reaching a minimum at 90% (w/w) dioxane, both rate constants increase again with further addition of dioxane. The kinetic ratio kI/kII is smaller than the statistical value 2.0, and is markedly affected both by solvent composition and temperature. The maximum concentration of the intermediate half ester decreases with increasing dioxane content. The observed activation energies EI and EII of the two steps of the reaction are largely dependent on temperature as well as solvent composition indicating a mixed type of bond fission represented by the AAl 1 and AAC 2 mechanisms, whose relative contributions in the overall rate constants kI and kIIcould be calculated on the basis of the number of water molecules incorporated in the corresponding transition states. The effect of bulk dielectric constant on the reaction rate was investigated in the light of the available electrostatic theories and showed the reaction to be an ion-molecular dipole type of interaction. The activation thermodynamic parameters were computed and discussed as criteria of solvent effect and mechanism.

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.

On the Role of Marangoni Effects on the Critical Heat Flux for Pool Boiling of Binary Mixtures

1996 ◽  
Vol 118 (1) ◽  
pp. 103-109 ◽  
Author(s):  
W. R. McGillis ◽  
V. P. Carey
Keyword(s):  
Surface Tension ◽  
Heat Flux ◽  
Binary Mixtures ◽  
Critical Heat Flux ◽  
Full Range ◽  
Pool Boiling ◽  
Marangoni Effect ◽  
Restoring Force ◽  
Marangoni Effects

The Marangoni effect on the critical heat flux (CHF) condition in pool boiling of binary mixtures has been identified and its effect has been quantitatively estimated with a modified model derived from hydrodynamics. The physical process of CHF in binary mixtures, and models used to describe it, are examined in the light of recent experimental evidence, accurate mixture properties, and phase equilibrium revealing a correlation to surface tension gradients and volatility. A correlation is developed from a heuristic model including the additional liquid restoring force caused by surface tension gradients. The CHF condition was determined experimentally for saturated methanol/water, 2-propanol/water, and ethylene glycol/water mixtures, over the full range of concentrations, and compared to the model. The evidence in this study demonstrates that in a mixture with large differences in surface tension, there is an additional hydrodynamic restoring force affecting the CHF condition.

Molecular Dynamics Simulations for Loading-Dependent Diffusion of CO2, SO2, CH4, and Their Binary Mixtures in ZIF-10: The Role of Hydrogen Bond

Langmuir ◽  
2017 ◽  
Vol 33 (42) ◽  
pp. 11543-11553 ◽  
Author(s):  
Li Li ◽  
Deshuai Yang ◽  
Trevor R. Fisher ◽  
Qi Qiao ◽  
Zhen Yang ◽  
...  
Keyword(s):  
Molecular Dynamics ◽  
Hydrogen Bond ◽  
Molecular Dynamics Simulations ◽  
Binary Mixtures ◽  
Dynamics Simulations

The role of hydrogen bonding in alginate/poly(acrylamide-co-dimethylacrylamide) and alginate/poly(ethylene glycol) methyl ether methacrylate-based tough hybrid hydrogels

RSC Advances ◽  
2015 ◽  
Vol 5 (71) ◽  
pp. 57678-57685 ◽  
Author(s):  
Zhi Wei Low ◽  
Pei Lin Chee ◽  
Dan Kai ◽  
Xian Jun Loh
Keyword(s):  
Hydrogen Bonding ◽  
Elastic Modulus ◽  
Ethylene Glycol ◽  
Methyl Ether ◽  
Poly Ethylene Glycol ◽  
Hybrid Hydrogels ◽  
Poly Ethylene ◽  
Glycol Methyl Ether ◽  
Poly Acrylamide

Hybrid hydrogels, with an elastic modulus and compressive toughness of 350 kPa and 70 J m−3, was synthesized and reported here.

The effects of osmotic pressure changes on the germination of Dictyostelium discoideum spores

1977 ◽  
Vol 23 (9) ◽  
pp. 1170-1177 ◽  
Author(s):  
David A. Cotter
Keyword(s):  
Ethylene Glycol ◽  
Dictyostelium Discoideum ◽  
Room Temperature ◽  
Thermal Inactivation ◽  
Sucrose Concentration ◽  
Lag Phase ◽  
Activation Process ◽  
Sucrose Solutions ◽  
Spore Population ◽  
Pressure Changes

Polyalcohols such as ethylene glycol and glycerol at 3 M penetrate and activate spores of Dictyostelium discoideum incubated at room temperature. Higher concentrations of ethylene glycol result in lysis upon suspension of spores in dilute phosphate buffer. Erythritol and arabitol at 3 M do not penetrate or activate D. discoideum spores.Air-dried spores or those incubated in 2 M sucrose solutions are not activated with the usual heat treatment of 45 °C for 30 min. The plasmolyzed spores are activated at temperatures above 45 °C when heated in the presence of 2 M sucrose for 30 min. The temperature for maximum activation and the temperature for thermal inactivation of spores are raised 7–10 °C in high sucrose concentrations. Long-term incubation of heat-activated spores in 2 M sucrose solutions does not result in a return to dormancy.Moderate sucrose concentrations near 0.2 M do not block the heat-induced activation process but must be removed from the spore population to prevent a return to dormancy within 6 h. Other polyhydric compounds at 0.25 M concentration also cause spore deactivation within 6 h of room temperature incubation. Oxygen uptake of spores undergoing deactivation in 0.18 M sucrose is inhibited as compared to control levels. Moderate concentrations of sucrose do not block the early events of postactivation lag and the spores accumulate at the end of the lag phase. The longer the spores remain unswollen at the end of the postactivation lag phase, the greater the percentage of spores which return to dormancy. The effects of moderate sucrose concentration (lowered water activity) are not duplicated by the same quantity of Ficoll, indicating that the colligative properties of the sucrose solutions are responsible for deactivation.

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