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.

Switchover of reactions of solvated electrons with nitrate ions and ammonium ions in propanol–water solvents

1993 ◽  
Vol 71 (9) ◽  
pp. 1297-1302 ◽  
Author(s):  
Tae Bum Kang ◽  
Gordon R. Freeman
Keyword(s):  
Rate Constants ◽  
Pure Water ◽  
Reaction Rates ◽  
Binary Solvents ◽  
Ammonium Ions ◽  
Concentrated Solutions ◽  
Solvated Electrons ◽  
Reaction Rate Constants ◽  
Water Solvent ◽  
Arrhenius Temperature

The reaction rate constants of [Formula: see text] with ammonium nitrate (~ 0.1 mol m−3) in 1-propanol-water and 2-propanol–water binary solvents correspond to [Formula: see text] reaction in the water-rich solvents, and to [Formula: see text] reaction in alcohol-rich solvents. The overall rate constant is smaller in solvents with 40–99 mol% water, with a minimum at 70 mol% water. The Arrhenius temperature coefficient is 26 kJ mol−1 in each pure propanol solvent, increases to 29 kJ mol−1 at 40 mol% water, then decreases to 17 kJ mol−1 in pure water solvent. The high reaction rates in the single component solvents, alcohol or water, are limited mainly by solvent processes related to shear viscosity (diffusion) and dielectric relaxation (dipole reorientation). Rate constants reported for concentrated solutions (50–1000 mol m−3) of ammonium and nitrate salts in methanol (Duplâtre and Jonah. J. Phys. Chem. 95, 897 (1991)) have been quantitatively reinterpreted in terms of the ion atmosphere model.

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 ions in isobutanol/water mixed solvents

1994 ◽  
Vol 72 (4) ◽  
pp. 1083-1093 ◽  
Author(s):  
Ruzhong Chen ◽  
Yuris Avotinsh ◽  
Gordon R. Freeman
Keyword(s):  
Proton Transfer ◽  
Pure Water ◽  
Mixed Solvents ◽  
Transition Metal Ions ◽  
Dielectric Relaxation Time ◽  
Solvated Electrons ◽  
Neutral Species ◽  
Water Solvent ◽  
Solvation Structure ◽  
Hydrogen Bonded

The effective reaction radii KRr, where Rr is the reactive encounter radius and K is the probability of reaction per encounter, for [Formula: see text] with [Formula: see text], are all 0.7 ± 0.1 nm in isobutanol containing 10–20 mol% water. The value remains at 0.7 ± 0.1 nm for [Formula: see text] in pure isobutanol, and for the two transition metal ions in pure water solvent. The value for [Formula: see text] reduces to 0.35 nm in pure isobutanol and pure water solvents, whereas for [Formula: see text] in pure water solvent it is only 0.14 nm and 2.6 × 10−5 nm, respectively. The low reactivity of [Formula: see text] with [Formula: see text] in water is attributed to the symmetry of the hydrogen-bonded solvation structure of [Formula: see text] in water, and the higher reactivity of [Formula: see text] is attributed to the lower symmetry of its hydrogen-bonded solvation structure. The [Formula: see text] ions have no low-lying orbital for an electron to occupy, so either reaction occurs by proton transfer to the electron site or the neutral species must decompose. We suggest that the proton transfer or the decomposition of the neutral species is facilitated by an unsymmetrical solvation structure.Reaction of [Formula: see text] in Al(ClO4)3 solutions in water is due mainly to [Formula: see text] from hydrolysis of [Formula: see text] and partly to partially hydroxylated aluminum(III) species. Reaction of [Formula: see text] with [Formula: see text] itself appears to be negligible in water. The reactivity of the solutions of Al(ClO4)3 in isobutanol-rich solvents is 3–5 times greater than that in water.In pure C1 to C4 1-alcanol solvents the value of [Formula: see text] increases linearly with the dielectric relaxation time τ1 of the solvent. In these solvents the probability of permanent capture per encounter increases approximately as the square of the encounter duration.

Solvent effects on the reactivity of solvated electrons with organic solutes in 1-butylamine–water mixtures

1996 ◽  
Vol 74 (3) ◽  
pp. 300-306 ◽  
Author(s):  
Yixing Zhao ◽  
Gordon R. Freeman
Keyword(s):  
Solvent Effects ◽  
Rate Constants ◽  
Pure Water ◽  
Strong Dependence ◽  
Mixed Solvents ◽  
Reaction Rates ◽  
Organic Solutes ◽  
Rich Region ◽  
Water Solvent ◽  
Solvent Molecules

The values of the rate constants of the reactions of es− with the efficient scavengers nitrobenzene and acetone are ≥ 2 × 106 m3 mol−1 s−1 in the whole range of 1-butylamine–water mixtures at 298 K; the reaction rates in the mixed solvents vary approximately as the solvent fluidity. In pure butylamine at 298 K, k2(es− + nitrobenzene) = 84 × 106 m3 mol−1 s−1 and k2(es− + acetone) = 7.3 × 106 m3 mol−1 s−1. The values of the rate constants of the reactions of es− with the inefficient scavengers phenol and toluene are < 2 × 105 m3 mol−1 s−1 in the whole range of 1-butylamine–water mixtures at 298 K and have a maximum at 50 mol% water and a minimum at 99 mol% water. In pure 1-butylamine at 298 K, k2(es− + phenol) = 1.0 × 104 m3 mol−1 s−1 and k2(es− + toluene) = 0.28 × 104 m3 mol−1 s−1. The reaction rates with inefficient scavengers show strong dependence on the solvent composition and selective solvation of electron and scavenger. In the amine-rich region (0–30 mol% water), the rate constants increase with the increase of viscosity, indicating the chemical participation of solvent molecules in the reaction. In the water-rich region from 50 to 99 mol% water, the decrease of the rate constants indicates the nonhomogeneous solvation of the electrons by water and of the organic solutes by 1-butylamine. From 99 mol% to pure water the rate constant increases rapidly, which we attribute to insufficient 1-butylamine to coat the phenol or toluene molecules. The variation of the activation energies E2 for the efficient scavengers, 14–27 kJ mol−1, are similar to the variation of Eη in the mixed solvents. The values of E2 for the inefficient scavengers are from 15 to 38 kJ mol−1 for phenol and from 6 to 21 kJ mol−1 for toluene. Both k2 and E2 for the inefficient scavenger reactions show a correlation with the temperature coefficient −dEAmax/dT of the optical absorption of es− in the mixed solvents, but the reason is obscure. Key words: 1-butylamine–water solvent, solvated electron, organic solutes, reactivity, solvent effects.

Solvent structure effects on solvated electron reactions with ions in 2-butanol/water mixed solvents

1991 ◽  
Vol 69 (5) ◽  
pp. 884-892 ◽  
Author(s):  
Sedigallage A. Peiris ◽  
Gordon R. Freeman
Keyword(s):  
Rate Constant ◽  
Pure Water ◽  
Mixed Solvents ◽  
Reaction Rates ◽  
Bimolecular Reaction ◽  
Activation Energies ◽  
Solvated Electron ◽  
Polar Species ◽  
Water Solvent ◽  
Alcohol Water

The Smoluchowski–Debye–Stokes–Einstein equation for the rate constant k2 of a bimolecular reaction between charged or polar species[Formula: see text]was used to evaluate effects of bulk solvent properties on reaction rates of solvated electrons with [Formula: see text] and [Formula: see text] in 2-butanol/water mixed solvents. To explain detailed effects it was necessary to consider more specific behavior of the solvent. Rate constants k2, activation energies E2, and pre-exponential factors A2 of these reactions vary with the composition of 2-butanol/water mixtures. The values of E2 were in general similar to activation energies of ionic conductance EΛ0 of the solutions, except for much higher values of E2 of [Formula: see text] in alcohol-rich solvents and of [Formula: see text] in pure water solvent. The solvent apparently participates chemically in the [Formula: see text] reaction, and the [Formula: see text] reaction is multistep. Rate constant and conductance measurements of thallium acetate solutions in 2-butanol containing zero and 10 mol% water were complicated by the formation of ion clusters larger than pairs. Key words: alcohol/water mixed solvents, ions, reaction kinetics, solvated kinetics, solvated electron, solvent effects.

Solvent structure effects on solvated electron reactions in mixed solvents: positive ions in 1-propanol/water and 2-propanol/water

1991 ◽  
Vol 69 (1) ◽  
pp. 157-166 ◽  
Author(s):  
Sedigallage A. Peiris ◽  
Gordon R. Freeman
Keyword(s):  
Pure Water ◽  
Mixed Solvents ◽  
Reaction Rates ◽  
Mutual Diffusion ◽  
Residual Effects ◽  
Solvated Electron ◽  
Bulk Fluid ◽  
Positive Ions ◽  
Water Solvent ◽  
Alcohol Water

In models of the kinetics of chemical reactions in solution the solvent is commonly assumed to be a uniform continuum. An example is the Smoluchowski–Debye–Stokes–Einstein equation for the rate constant k2 of a bimolecular reaction between charged or polar species:[Formula: see text]where κ is the probability that a reactant encounter pair will react, R is the gas constant, T is the temperature, f is a factor that reflects the effect of electrostatic interaction between the reactants on their probability of attaining the closeness of approach rr at which reaction occurs, η is the solvent viscosity, and rd is the effective radius of the reactant entities for mutual diffusion. The equation is useful in evaluating effects of bulk fluid properties on reaction rates. Residual effects are attributed to more specific solvent behaviour.Rate constants k2, activation energies E2, and pre-exponential factors A2 of reactions of solvated electrons [Formula: see text] with [Formula: see text] [Formula: see text] and [Formula: see text] ions vary with the composition of 1-propanol/water and 2-propanol/water mixed solvents. Plots of k2η/fT against solvent composition are nonlinear and change with the solvent pair and with reactant pair. Measured molar conductivities [Formula: see text] [Formula: see text] [Formula: see text] and [Formula: see text] indicate that the values of rd for the mutual diffusion of the cations and anions have a minimum near 90 mol% water, and that the values in pure propanol-1 or −2 (150–190 pm) are larger than those in pure water solvent (26 pm for [Formula: see text] 70 pm for the metal ions). The liquid structure influences both the rate of diffusion and the probability of reaction of a reactant encounter pair. Key words: alcohol/water mixed solvents, positive ions, reaction kinetics, solvated electron, solvent effects.

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.

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>

scholarly journals The comparative study of linear solvatation energy relationship for the reactivity of pyridine carboxylic acids with diazodiphenylmethane in protic and aprotic solvents

2012 ◽  
Vol 77 (10) ◽  
pp. 1311-1338 ◽  
Author(s):  
Sasa Drmanic ◽  
Jasmina Nikolic ◽  
Aleksandar Marinkovic ◽  
Bratislav Jovanovic
Keyword(s):  
Solvent Effects ◽  
Kinetic Data ◽  
Aprotic Solvent ◽  
Isonicotinic Acid ◽  
Linear Regression Analysis ◽  
Multiple Linear Regression Analysis ◽  
Reaction Rates ◽  
Aprotic Solvents ◽  
Pyridine Carboxylic ◽  
The Comparative Study

Protic and aprotic solvent effects on the reactivity of picolinic, nicotinic and isonicotinic acid, as well as of some substituted nicotinic acids with diazodiphenylmethane (DDM) were investigated. In order to explain the kinetic results through solvent effects, the second-order rate constants for the reaction of the examined acids with DDM were correlated using the Kamlet-Taft solvatochromic equation. The correlations of the kinetic data were carried out by means of the multiple linear regression analysis and the solvent effects on the reaction rates were analyzed in terms of the contributions of the initial and the transition state. The signs of the equation coefficients support the already known reaction mechanism. The solvatation models for all the investigated acids are suggested and related to their specific structure.

ChemInform Abstract: SOLVATED ELECTRON REACTION RATES IN ALCOHOLS AND WATER. SOLVENT EFFECT

1977 ◽  
Vol 8 (5) ◽  
pp. no-no
Author(s):  
G. L. BOLTON ◽  
G. R. FREEMAN
Keyword(s):  
Solvent Effect ◽  
Reaction Rates ◽  
Solvated Electron ◽  
Water Solvent
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