Solvent assisted decomposition of the tetrahedral intermediate of the transesterification reaction to biodiesel production. A density functional study

Lima, Emmanuela Ferreira de; Carneiro, José Walkimar de M.; Fenollar-Ferrer, C.; Miertus, Stanislav; Zinoviev, Sergey; Tapanes, N. C. O.; Aranda, Donato Alexandre Gomes

doi:10.1016/j.fuel.2009.08.018

Cited by 10 publications

(2 citation statements)

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“…The literature [38][39][40][41] has shown that chemical characteristics and reactions can be influenced by the nature of the solvent used. In order to study the effect of the solvent, OCS hydrolysis via reactions (1) and (2) was examined in bulk water solvent using the COSMO model (dielectric constant ε=78.54), employing the geometries optimized in the gas phase.…”

Section: Effect Of the Solventmentioning

confidence: 99%

Density functional theory analysis of carbonyl sulfide hydrolysis: effect of solvation and nucleophile variation

2011

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The detailed mechanisms of the hydrolysis of carbonyl sulfide (OCS) by nucleophilic water and hydroxide ion in both the gas phase and bulk water solvent have been investigated using density functional theory. Various reaction channels on the potential surface have been identified. The thermodynamic results demonstrate that the hydrolysis of OCS by nucleophilic water and hydroxide ion should proceed more favorably at low temperature. The hydrolysis of OCS by the hydroxide ion is the main reaction channel from thermodynamic and kinetic perspectives, and the bulk solvent can influence the rate-determining step in this channel. However, the solvent barely modifies the activation energy of the rate-determining step. For the hydrolysis of OCS by nucleophilic water, the solvent does not modify the rate-determining step, and the corresponding activation energy of the rate-determining step barely changes. This bulk solvent effect suggests that most of the contribution of the solvent is accounted for by considering one water molecule and a hydroxide ion.

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Section: Effect Of the Solventmentioning

confidence: 99%

Density functional theory analysis of carbonyl sulfide hydrolysis: effect of solvation and nucleophile variation

2011

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“…However, many researches have shown that the chemical characteristic and reaction barrier in liquid‐phase environment are different from those in gas phase, namely, the reaction environments might change the chemical characteristic and reaction barrier, in which the solvent environment plays an important role. [25–36] Therefore, it is of great significance to study the detailed mechanism and kinetics of DMC formation both in gas phase and in liquid‐phase environment.…”

Section: Introductionmentioning

confidence: 99%

Atlas of head and neck surgery: Expert consult

Wein

2012

Head & Neck

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A density functional theory investigation on the mechanism and kinetics of dimethyl carbonate formation on Cu₂O catalyst

et al. 2012

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A theoretical analysis about the mechanism and kinetics of dimethyl carbonate (DMC) formation via oxidative carbonylation of methanol on Cu(2)O catalyst is explored using periodic density functional calculations, both in gas phase and in solvent. The effect of solvent is taken into account using the conductor-like screening model. The calculated results show that CO insertion to methoxide species to produce monomethyl carbonate species is the rate-determining step, the corresponding activation barrier is 161.9 kJ mol(-1). Then, monomethyl carbonate species reacts with additional methoxide to form DMC with an activation barrier of 98.8 kJ mol(-1), above reaction pathway mainly contributes to the formation of DMC. CO insertion to dimethoxide species to form DMC is also considered and analyzed, the corresponding activation barrier is 308.5 kJ mol(-1), suggesting that CO insertion to dimethoxide species is not competitive in dynamics in comparison with CO insertion to methoxide species. The solvent effects on CO insertion to methoxide species involving the activation barriers suggest that the rate-determining step can be significantly affected by the solvent, 70.2 kJ mol(-1) in methanol and 63.9 kJ mol(-1) in water, which means that solvent effect can reduce the activation barrier of CO insertion to methoxide species and make the reaction of CO insertion to methoxide in solvents much easier than that in gas phase. Above calculated results can provide good theoretical guidance for the mechanism and kinetics of DMC formation and suggest that solvent effect can well improve the performance of DMC formation on Cu(2)O catalyst in a liquid-phase slurry.

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Solvent assisted decomposition of the tetrahedral intermediate of the transesterification reaction to biodiesel production. A density functional study

Cited by 10 publications

References 41 publications

Density functional theory analysis of carbonyl sulfide hydrolysis: effect of solvation and nucleophile variation

Density functional theory analysis of carbonyl sulfide hydrolysis: effect of solvation and nucleophile variation

Atlas of head and neck surgery: Expert consult

A density functional theory investigation on the mechanism and kinetics of dimethyl carbonate formation on Cu₂O catalyst

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Solvent assisted decomposition of the tetrahedral intermediate of the transesterification reaction to biodiesel production. A density functional study

Cited by 10 publications

References 41 publications

Density functional theory analysis of carbonyl sulfide hydrolysis: effect of solvation and nucleophile variation

Density functional theory analysis of carbonyl sulfide hydrolysis: effect of solvation and nucleophile variation

Atlas of head and neck surgery: Expert consult

A density functional theory investigation on the mechanism and kinetics of dimethyl carbonate formation on Cu2O catalyst

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Product

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A density functional theory investigation on the mechanism and kinetics of dimethyl carbonate formation on Cu₂O catalyst