Solvent Influence on Rates and Mechanisms

Amis, Edward S.; Hinton, James F.

doi:10.1016/b978-0-12-057301-1.50010-6

Cited by 17 publications

(25 citation statements)

References 401 publications

(494 reference statements)

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“…1 and 2) It is well known that an increase in the organic component (acetone in this study) in a binary aquo-organic solvent mixture decreases the bulk dielectric constant (D) of the medium. The kinetic results of this study indicate that the rates of the reaction are faster in the solvent of low D. According to Amis' theory (11) of the effect of dielectric constant (on reaction rates), such results lead to the formulation of cation-dipole participation in the slow step.…”

Section: Effect Of Solventmentioning

confidence: 63%

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Methylene Blue - Ascorbic Acid: An Undergraduate Experiment in Kinetics

1997

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Clock reaction experiments with methylene blue (MB) and L-ascorbic acid (H2 A) were designed in aqueous sulfuric and hydrochloric acid media with a view to demonstrate and explain the concepts in chemical kinetics such as order of the reaction, effect of ionic strength, dielectric constant and temperature. On the basis of the obtained results, a plausible mechanism for the reduction of MB by H2 A has been proposed.

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Section: Effect Of Solventmentioning

confidence: 63%

“…First order dependence on [H 2 A] and fractional order dependence on [MB] coupled with the results obtained during studies of the effects of ionic strength, acid, and solvents indicate that the most plausible mechanism involves a cation-dipole type of species (11) in the ratedetermining step (scheme I):…”

Section: IImentioning

confidence: 96%

Methylene Blue - Ascorbic Acid: An Undergraduate Experiment in Kinetics

1997

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“…It is well known for a longer time that solvent plays a vital role to affect the rate of a chemical reaction. [30][31][32] A perusal of literature revealed that a solvent may influence the reaction rates either through equilibrium solvent or frictional solvent properties. 31 It is important to know that equilibrium solvent effects are derived on the basis of transition state theory (TST), while frictional solvent effects (like density, internal pressure, viscosity, surface tension, etc.)…”

Section: Kinetic Correlation Of Solvent Properties With Reactivitymentioning

confidence: 99%

“…30 Accordingly, we have initially tried to test the rate data with the bulk dielectric constant (D) using the semiquantitative relationships developed by Edward Amis, Laidler and Eyring, Kirkwood, and many others. [30][31][32] Laidler-Eyring's equation for ion-dipole reactions is given as…”

Section: Kinetic Correlation Of Solvent Properties With Reactivitymentioning

confidence: 99%

Trichloroisocyanuric acid (TCCA) and carboxamide interactions in TCCA/NaNO₂ triggered nitration of pyrrole and indole in aqueous aprotic media: A kinetic correlation of solvent properties with reactivity

Duguta

Muddam

Kamatala

et al. 2020

Int J of Chemical Kinetics

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This study deals with the trichloroisocyanuric acid (TCCA) interactions with carboxamides like formamide (FMA), N,N′-dimethyl formamide (DMF), and N,N′dimethyl acetamide (DMA) interactions during the nitration of heterocyclic compounds (HC) like pyrrole and indole in the presence of excess of [NaNO 2 ] over the concentrations of all other reactants. All the reactions were performed in aqueous acetonitrile media containing carboxamide under acid-free conditions. Kinetics of the reactions revealed first order in [nitrating agent] and [HC] under otherwise similar conditions. To gain an insight into the reactive species and role of added carboxamide (FAA, DMF, DMA, etc.), the observed rates of the nitration reaction (log k) were analyzed as a function of (1/D), ([D − 1]/[2D + 1]), mole fraction (n x), and volume (%) of carboxamide, 1/viscosity, density refractive index function), and Hildebrand solubility parameter plots. Linear regression analysis gave very good correlation coefficients (R 2 values), which indicate the importance of several solvent properties in addition to the role of dielectric constant (D) of the reaction media. Multiple linear solvent energy relationships suggested by Abraham, Koppel, Palm, and Taft also afforded very good correlation coefficient (R 2 values), showing the importance of cumulative effect of solvent properties. Besides these features, the negative entropies of activation (∆S #) suggest greater solvation in the transition state. Isokinetic temperature (β) values for different protocols were very close to the experimental temperature range (303-323 K), indicating the importance of both enthalpy and entropy factors in controlling the reaction.

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“…On the one hand, due to the extremely low dielectric constant of water in the supercritical region, a low solubility of intermediate products and metallic oxide was obtained. On the other hand, depending on the Born-type equation [33], the reaction rate is inversely proportional to dielectric constant, thus extremely low dielectric constant leads to fast hydrolysis, dehydration, and nucleation rate compared to them at the subcritical region. These can explain the formation of high crystallinity products.…”

Section: Effects Of Temperaturementioning

confidence: 99%

One-pot synthesis of nano titanium dioxide in supercritical water

Sun

Wang

et al. 2020

Nanotechnology Reviews

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AbstractSupercritical hydrothermal synthesis of nanosized metal oxides is of great interest for scholars due to its one-pot and readily realizing commercial production process. Hydrothermal synthesis of nanosized TiO2 in subcritical and supercritical water was investigated with different reaction temperatures (250–450°C), time (3–10 min), precursor species (Ti(SO4)2, TiCl4), and the addition of a surfactant (CH3(CH2)5NH2). TiO2 synthesized under supercritical state has a higher degree of crystallinity when compared with TiO2 obtained from subcritical state, which is attributed to a higher reaction rate. Extending reaction time from 3 to 10 min leads to the growth of crystal and broader size distribution (36.66 ± 8.5 nm). More uniform products can be obtained when Ti(SO4)2 acting as the precursor compared with TiCl4 being the precursor. The application of surfactant CH3(CH2)5NH2 in the synthesis makes chemical bonding between the particle surface and organic ligand. It affects the growth direction of TiO2 crystal; as a result, rod-like TiO2 crystal is obtained.

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Solvent Influence on Rates and Mechanisms

Cited by 17 publications

References 401 publications

Methylene Blue - Ascorbic Acid: An Undergraduate Experiment in Kinetics

Methylene Blue - Ascorbic Acid: An Undergraduate Experiment in Kinetics

Trichloroisocyanuric acid (TCCA) and carboxamide interactions in TCCA/NaNO₂ triggered nitration of pyrrole and indole in aqueous aprotic media: A kinetic correlation of solvent properties with reactivity

One-pot synthesis of nano titanium dioxide in supercritical water

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Solvent Influence on Rates and Mechanisms

Cited by 17 publications

References 401 publications

Methylene Blue - Ascorbic Acid: An Undergraduate Experiment in Kinetics

Methylene Blue - Ascorbic Acid: An Undergraduate Experiment in Kinetics

Trichloroisocyanuric acid (TCCA) and carboxamide interactions in TCCA/NaNO2 triggered nitration of pyrrole and indole in aqueous aprotic media: A kinetic correlation of solvent properties with reactivity

One-pot synthesis of nano titanium dioxide in supercritical water

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Product

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Trichloroisocyanuric acid (TCCA) and carboxamide interactions in TCCA/NaNO₂ triggered nitration of pyrrole and indole in aqueous aprotic media: A kinetic correlation of solvent properties with reactivity