Solvent Effects on Reactivity of Solvated Electrons with Nitrate Ion and on Electrolyte Conductivity in C1 to C10 n-Alcohols

1995 ◽  
Vol 99 (14) ◽  
pp. 4970-4975 ◽  
Author(s):  
Ruzhong Chen ◽  
Gordon R. Freeman
Keyword(s):  
Solvent Effects ◽  
Solvated Electrons ◽  
Nitrate Ion ◽  
Electrolyte Conductivity

Solvent effects on the reactivity of solvated electrons with ammonium and nitrate ions in 1-butanol–water solvents

1993 ◽  
Vol 71 (9) ◽  
pp. 1303-1310 ◽  
Author(s):  
Ruzhong Chen ◽  
Gordon R. Freeman
Keyword(s):  
Solvent Effects ◽  
Pure Water ◽  
Reaction Rates ◽  
Dielectric Relaxation Time ◽  
Unusual Behavior ◽  
Solvated Electrons ◽  
Water Solvent ◽  
Electrical Conductances ◽  
Average Size ◽  
Effective Reaction

Values of the rate constants, k2 (106 m3 mol−1 s−1), of solvated electrons,[Formula: see text] with several related salts, in pure water and pure 1-butanol solvents at 298 K are, respectively, as follows: LiNO3, 9.2, 0.19; NH4NO3, 10, 8.3; NH4ClO4, 1.5 × 10−3, 12 in 20 mol% water; LiClO4, 1.0 × 10−4, < 1.0 × 10−4. The value of [Formula: see text] in water solvent is 48 times larger than that in 1-butanol solvent, whereas [Formula: see text] in water is 10−4 times smaller than the value in 1-butanol. This enormous reversal of solvent effects on [Formula: see text] reaction rates is the first observed for ionic reactants. The solvent participates chemically in the [Formula: see text] reaction, and the overall rate constant increases with increasing viscosity and dielectric relaxation time. This unusual behavior is attributed to a greatly increased probability of reaction of an encounter pair with increasing duration of the encounter. Effective reaction radii κRr for [Formula: see text] and [Formula: see text] were estimated with the aid of measured electrical conductances of the salt solutions in all the solvents. Values of κRr are (2–7) × 10−10 m, except for NH4,s+ in 100 and 99 mol% water, which are 2.6 and 2.7 × 10−14 m, respectively. The effective radii of the ions for mutual diffusion increase with increasing butanol content of the solvent, from ~50 pm in water to ~150 pm in 1-butanol, due to the increasing average size of the molecules that solvate the ions.

Solvent effects on the reactivity of solvated electrons with ions in tert-butanol/water mixtures

1995 ◽  
Vol 73 (3) ◽  
pp. 392-400 ◽  
Author(s):  
Yixing Zhao ◽  
Gordon R. Freeman
Keyword(s):  
Solvent Effects ◽  
Pure Water ◽  
Solvated Electrons ◽  
Rich Region ◽  
Tert Butanol ◽  
Einstein Model ◽  
Activation Energy For Diffusion ◽  
Minimum Number ◽  
Solvent Molecules ◽  
Effective Reaction

Reactions of [Formula: see text] with the ions [Formula: see text] showed different variations of rate with solvent composition in tert-butanol/water mixtures from 0 to 100 mol% water. In pure tert-butanol solvent at 298 K the respective values of k2 (106 m3 mol−1 s−1) are 3.2, 13, and 42. The estimated value of reaction radius Rr depends on the minimum number of solvent molecules needed between [Formula: see text] and the reactant ion to attain the static values of ε of the bulk solvent used in the calculation of the Debye factor f; Rr is assumed to be larger in the alcohol-rich region than in the water-rich region, because the solvent molecules are larger. The Smoluchowski–Debye–Nernst–Einstein model is used to evaluate the effective reaction radius κRr, where κ is the probability of reaction per encounter; κRr decreases from pure tert-butanol to pure water. In the water-rich region the activation energies E2 of the efficient reactions, 11–24 kJ mol−1, are similar to EΛ0 of the reactant electrolyes, 12–23 kJ mol−1. For the inefficient reactant [Formula: see text] E2 = 30 kJ mol−1. The high values of E2 = 43–53 kJ mol−1 in pure tert-butanol solvent are attributed to a high activation energy for diffusion of [Formula: see text] in this solvent. Keywords:tert-butanol/water solvents, solvated electron, ions, reactivity, solvent effects.

Solvent effects on the reactivity of solvated electrons with charged solutes in methanol/water and ethanol/water mixed solvents

1990 ◽  
Vol 94 (12) ◽  
pp. 4891-4896 ◽  
Author(s):  
Charles C. Lai ◽  
Gordon R. Freeman
Keyword(s):  
Solvent Effects ◽  
Mixed Solvents ◽  
Solvated Electrons

Solvent effects on the reactivity of solvated electrons with organic solutes in methanol/water and ethanol/water mixed solvents

1990 ◽  
Vol 94 (1) ◽  
pp. 302-308 ◽  
Author(s):  
Charles C. Lai ◽  
Gordon R. Freeman
Keyword(s):  
Solvent Effects ◽  
Mixed Solvents ◽  
Organic Solutes ◽  
Solvated Electrons

Solvent effects on the reactivity of solvated electrons with in C1 to C4 alcohols

1995 ◽  
Vol 73 (2) ◽  
pp. 284-288 ◽  
Author(s):  
Yixing Zhao ◽  
Gordon R. Freeman
Keyword(s):  
Solvent Effects ◽  
Trap Depth ◽  
Secondary Alcohols ◽  
Primary Alcohols ◽  
Solvated Electron ◽  
Solvated Electrons ◽  
Coulombic Repulsion ◽  
Keywords Alcohol ◽  
Alcohol Solvents ◽  
Effective Reaction

The rate constants [Formula: see text] in pure C1 to C4 alcohol solvents at 298 K increase with increasing viscosity and decreasing permittivity. Thus the reactivity increases with decreasing diffusivity and increasing coulombic repulsion, so the Debye–Smoluchowski model does not apply. The effective reaction radius κRr increases with decrease of effective trap depth Er/τ of the electrons in the solvent: κRr = CτRr(Er/τ)pτ. Values of κRr and Er/τ change with temperature, and values of Pτ fall in four categories: ∼0.0 for water and methanol; ∼1.3 for primary alcohols; 0.6 for secondary alcohols; 1.8 for tert-butanol. The C—H groups participate in the [Formula: see text] reaction. Keywords: alcohol solvents, solvated electron, nitrate ion, reactivity, solvent effects.

Determination of Nitrate Ion in Cheese and Sake

2020 ◽  
Vol 61 (6) ◽  
pp. 229-234
Author(s):  
Takahiro Sasaki ◽  
Shoichi Tahara ◽  
Ritsuko Toyohara ◽  
Mari Morikawa ◽  
Narue Sakamaki ◽  
...  
Keyword(s):  
Nitrate Ion

Kinetic Solvent Effects in Organic Reactions

2017 ◽  
Author(s):  
Belinda Slakman ◽  
Richard West
Keyword(s):  
Solvent Effect ◽  
Reaction Kinetics ◽  
Computational Methods ◽  
High Throughput ◽  
Kinetic Modeling ◽  
Solvent Effects ◽  
Reaction Rates ◽  
Prior Work ◽  
Solvent Phase ◽  
High Throughput Manner

<div> <div> <div> <p>This article reviews prior work studying reaction kinetics in solution, with the goal of using this information to improve detailed kinetic modeling in the solvent phase. Both experimental and computational methods for calculating reaction rates in liquids are reviewed. Previous studies, which used such methods to determine solvent effects, are then analyzed based on reaction family. Many of these studies correlate kinetic solvent effect with one or more solvent parameters or properties of reacting species, but it is not always possible, and investigations are usually done on too few reactions and solvents to truly generalize. From these studies, we present suggestions on how best to use data to generalize solvent effects for many different reaction types in a high throughput manner. </p> </div> </div> </div>

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