Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene

Tucceri, María E.; Badenes, María Paula; Cobos, Carlos

doi:10.1021/jp406931q

Cited by 10 publications

(12 citation statements)

References 45 publications

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“…[1] In this regard, poly(o-aminophenol) (PoAP) exhibits several advantages with respect to other electrosynthesized polymers because it shows conductive or insulating properties under electropolymerization in acidic and neutral/basic media, respectively. [2,3] As recently reported in literature, [4,5] this film is able to immobilize biological macromolecules and can be also employed to develop stable electrocatalysts for oxygen reduction because of its strong acceptor binding with several metal cations. In the sensor field, the insulating properties of poly(o-aminophenol) have found increasingly interest in preventing the biosensor from fouling and removing the interference from electroactive species, as essentially required for obtaining a selective current response.…”

Section: Introductionmentioning

confidence: 76%

“…In the sensor field, the insulating properties of poly(o-aminophenol) have found increasingly interest in preventing the biosensor from fouling and removing the interference from electroactive species, as essentially required for obtaining a selective current response. [5] According to previous studies based on combined experiments, [6][7][8] hypotheses were advanced on the composition of the very thin, insulating, PoAP grown on platinum by cyclic voltammetry (CV).…”

Section: Introductionmentioning

confidence: 99%

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XPS, AFM, and electrochemical investigation on the inner composition of insulating poly(o‐aminophenol), PoAP, deposited on platinum by CV, as a function of the number of cycles

Carbone

Ciriello

Guerrieri

et al. 2015

Surface & Interface Analysis

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The finite electrosynthesis, requiring 20 voltammetric cycles at neutral pH, of insulating poly(o-aminophenol) (PoAP)and its polymerization mechanism and chemical structure up to the outermost surface were reported in previous work. By reducing the number of voltammetric cycles, XPS, atomic force microscopy, and electrochemical experiments were here confined to partially grown PoAP to better understand the role of the platinum surface on the initial adhesion mechanism and polymer growth. XPS results from reduced number and conventional 20 cycles show that PoAP composition is the same at any cycle. The main differences imaged by atomic force microscopy between 1, 5, and 20 cycles are on the amount of 'small-sized particles' adsorbed on platinum prone to 'fill' the empty sites. The progressive filling of the platinum sites with cycles was also proved by electrochemical test with potassium-ferricyanide. These new results add valuable information, which sustain previous hypotheses on the growth process of PoAP chains, their composition, and lateral alignment. Some questions, concerning the identification of PoAP anchoring bonds on platinum, lateral H-bonds with water, and inter-chains interactions, still remain unanswered and will be further addressed by the employment of new advanced means of investigation already in progress.

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Section: Introductionmentioning

confidence: 76%

Section: Introductionmentioning

confidence: 99%

XPS, AFM, and electrochemical investigation on the inner composition of insulating poly(o‐aminophenol), PoAP, deposited on platinum by CV, as a function of the number of cycles

Carbone

Ciriello

Guerrieri

et al. 2015

Surface & Interface Analysis

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“…Because of the large uncertainties observed in the kinetic data reported for 2-chloropropene and 2-bromopropene decomposition reactions, quantum chemical and theoretical kinetic studies have been recently performed to elucidate these discrepancies. , To clarify the above-mentioned differences, the unimolecular reaction rate theory combined with potential energy surfaces derived via reliable quantum mechanical calculations were employed in the present study. An analysis of the energetics of the reaction channels ()–(), and the prediction of the rate constants over wide ranges of temperatures and pressures, are included in this investigation.…”

Section: Introductionmentioning

confidence: 99%

Thermal Decomposition of 3-Bromopropene. A Theoretical Kinetic Investigation

et al. 2016

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A detailed kinetic study of the gas-phase thermal decomposition of 3-bromopropene over wide temperature and pressure ranges was performed. Quantum chemical calculations employing the density functional theory methods B3LYP, BMK, and M06-2X and the CBS-QB3 and G4 ab initio composite models provide the relevant part of the potential energy surfaces and the molecular properties of the species involved in the CH2═CH-CH2Br → CH2═C═CH2 + HBr (1) and CH2═CH-CH2Br → CH2═CH-CH2 + Br (2) reaction channels. Transition-state theory and unimolecular reaction rate theory calculations show that the simple bond fission reaction ( 2 ) is the predominant decomposition channel and that all reported experimental studies are very close to the high-pressure limit of this process. Over the 500-1400 K range a rate constant for the primary dissociation of k2,∞ = 4.8 × 10(14) exp(-55.0 kcal mol(-1)/RT) s(-1) is predicted at the G4 level. The calculated k1,∞ values lie between 50 to 260 times smaller. A value of 10.6 ± 1.5 kcal mol(-1) for the standard enthalpy of formation of 3-bromopropene at 298 K was estimated from G4 thermochemical calculations.

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“…The geometric parameters of the reactant, transition state, and products of the studied reaction were fully optimized using density functional theory (DFT) with the M05–2X functional and the 6–31+G( d , p ) basis set. The M05–2X functional is a highly nonlocal functional that has been specially designed to reproduce the thermodynamics and kinetics of chemical reactions with accuracy close to that experimentally observed , and has been successfully used in recent kinetic studies . Each structure was characterized as a minimum or a saddle point of first order by analytical frequency calculations.…”

Section: Computational Detailsmentioning

confidence: 99%

Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

Quíjano

Ruíz

Notario

et al. 2014

Int J of Chemical Kinetics

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An experimental study of the thermal decomposition of a β-hydroxy alkene, 3-methyl-3-buten-1-ol, in m-xylene solution, has been carried out at five different temperatures in the range of 513.15-563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s −1 ) = (25.65 ± 1.52) − (17,944 ± 814) (kJ·mol −1 )·T −1 . A computational study has been carried out at the M05-2X/6-31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one-step process proceeding through a six-membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811-1816 for the thermal decomposition of 3-buten-1-ol, in m-xylene solution. We can conclude that in the compound studied in this work, 3-methyl-3-buten-1-ol, the effect of substitution at position 3 by a weakly activating CH 3 group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition. C

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Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene

Cited by 10 publications

References 45 publications

XPS, AFM, and electrochemical investigation on the inner composition of insulating poly(o‐aminophenol), PoAP, deposited on platinum by CV, as a function of the number of cycles

XPS, AFM, and electrochemical investigation on the inner composition of insulating poly(o‐aminophenol), PoAP, deposited on platinum by CV, as a function of the number of cycles

Thermal Decomposition of 3-Bromopropene. A Theoretical Kinetic Investigation

Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

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