Experimental and Theoretical Study of the Kinetics and Mechanism of the Reaction of Chlorine Atoms with CH3CHClCH3 and CD3CDClCD3

Sarzyński, Dariusz; Fojcik, Łukasz; Latajka, Zdzisław

doi:10.1021/acs.jpca.7b10031

Cited by 4 publications

(8 citation statements)

References 35 publications

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“…Similar to reaction R1, reaction R2 had negative temperature dependency both experimentally and computationally over the studied temperature range, which is due to the formation of more stabilized prereactive complexes. Sarzynḱi et al 23 measured the rate coefficient for reaction R2 and observed a positive temperature dependency, which contradicts our reported results. They also have studies of reaction R2 using the RR method with ethane as reference.…”

Section: Relative Rate Measurements For 2-chloropropanecontrasting

confidence: 99%

“…While the room temperature rate coefficients are in reasonable agreement with the present values, the positive temperature dependence may be attributed to any of the mentioned differences in the experimental conditions. Also, Sarzynḱi et al 23 theoretically explored the mechanism for the hydrogen abstraction of 2-CP by Cl atoms. In their investigation, they observed the rate coefficient for the abstraction of hydrogen attached to the secondary carbon to be decreasing with increase temperature.…”

Section: Relative Rate Measurements For 2-chloropropanementioning

confidence: 99%

“…They have used ethylene and ethyl chloride as reference compounds and reported the rate coefficient at 296 K to be (2.01 ± 0.49) × 10 −11 cm 3 molecule −1 s −1 . Sarzynski et al 23 measured the temperature dependent rate coefficients for the reaction of 2-CP with Cl atoms in the temperature range 298− 528.5 K and at 100 Torr of pressure using the relative rate technique with ethane as a reference compound. Also, they have measured the rate coefficients for the deuterated 2-CP in the same experimental conditions.…”

Section: Introductionmentioning

confidence: 99%

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Cl Atom Initiated Photo-oxidation of Mono-chlorinated Propanes To Form Carbonyl Compounds: A Kinetic and Mechanistic Approach

Kumar

Rajakumar

2019

J. Phys. Chem. A

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Cl atom initiated photo-oxidation of monochlorinated propanes to form the carbonyl compounds was investigated. Propionaldehyde and acetone were identified to be major products in the oxidation of 1-chloropropane and 2-chloropropane, respectively. The complete product analyses were carried out using gas chromatography–mass spectrometry (GC–MS) and gas chromatography–infrared spectroscopy (GC–IR) as analytical tools, and an appropriate oxidation mechanism was proposed on the basis of the product analyses. The temperature dependent rate coefficients for the reactions of Cl atoms with 1-chloropropane (1-CP) and 2-chloropropane (2-CP) were measured experimentally in the gas phase, using the relative rate method in the temperature range 268–363 K and at 1 atm pressure. Ethane, ethylene, and ethyl acetate were used as reference compounds. The obtained rate coefficients for the reactions of Cl atoms with 1-CP and 2-CP at room temperature (298 K) and at 1 atm pressure were (4.64 ± 0.70) × 10–11 and (2.57 ± 0.44) × 10–11 cm3 molecule–1 s–1, respectively. Furthermore, to complement our experimentally obtained results, computational calculations were performed for these reactions using canonical variational transition state theory (CVT) with small curvature tunneling (SCT) in combination with the CCSD/cc-pVDZ//MP2/6-31+G(d,p) level of theory. Detailed discussion on feasibility of the reactions, branching ratios, degradation mechanism, and atmospheric implications are discussed in this manuscript.

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Section: Relative Rate Measurements For 2-chloropropanecontrasting

confidence: 99%

Section: Relative Rate Measurements For 2-chloropropanementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Cl Atom Initiated Photo-oxidation of Mono-chlorinated Propanes To Form Carbonyl Compounds: A Kinetic and Mechanistic Approach

Kumar

Rajakumar

2019

J. Phys. Chem. A

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“…at 296 K, Wallington et al 15 . at 295 K, and the temperature dependences of k H determined by Kumar and Rajakumar 16 in the temperature range of 263–363 K. For the studied reaction, we observed a positive temperature dependence which is not in line with the experimental temperature dependence of k H as determined by Kumar and Rajakumar 16 in the temperature range of 263–363 K. The same is true for the reaction of CH 3 CHClCH 3 + Cl 43 . We determined a positive temperature dependence in the temperature range of 298–528 K, while Kumar and Rajakumar 16 recorded the opposite temperature dependence in the temperature range of 263–363 K.…”

Section: Resultscontrasting

confidence: 65%

Theoretical and experimental studies of the kinetics of the reaction of 1‐chloropropane and fully deuterated 1‐chloropropane with atomic chlorine

Fojcik

Sarzyński

Dryś

et al. 2021

Int J of Chemical Kinetics

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The overall rate constant for H‐abstraction (kH) from CH3CH2CH2Cl and D‐abstraction (kD) from CD3CH2CD2Cl by chlorine atoms is described by the formulas: kH=false(6.48−1.19+1.45false)×10−12·(T298)(1.810.28em±0.28em0.15)·exp(597±0.28em62)Tcnormalm3moleculnormale−1normals−1and kD=false(1.45−0.27+0.33false)×10−12·exp(801±62)Tcnormalm3moleculnormale−1normals−1, respectively. The results of the experiment show that the value of the kinetic isotope effect (kH/kD) for the overall rate constants is also temperature dependent in the temperature range of 298–550 K and can be expressed as kHkD=false(4.34−1.27+1.80false)·(T298)−0.88±0.26·expfalse(−1950.28em±0.28em105Tfalse). The titled reaction was also studied theoretically for the same range of temperatures and with both isotope substituents, just like in the experiment. The computations were made using the MP2 method and the aug‐cc‐pVDZ basis set. This paper presents detailed results relating to structural parameters of each of the compounds, complexes, and all energy stages important to the reaction mechanism analysis. It also describes all possible individual channels of the process and their feasibilities. In addition, a kinetic analysis of the process was carried out with branching ratio calculations. The results presented here have been compared with those discussed in a paper published earlier, in which the same process was investigated.

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“…Conforme discussões na literatura, isto geralmente ocorre em reações que apresentam um pré-complexo (aqui representado por IM1) e quando o estado de transição correspondente apresenta energia menor que aquela dos reagentes. 87,88 Este fato justifica também a diminuição da constante de velocidade com o aumento de temperatura, o qual foi observado na Tabela 20. Para concluir, as energias de ativação envolvidas nas duas etapas da reação CH 4 + Au + → IM2 → AuCH 2 + + H 2 são de -19,4 e 66,0 kcal mol -1 , respectivamente.…”

Section: Resultados E Discussõesunclassified

Métodos avançados da química quântica relativística aplicados em estudos de cinética química

Santiago¹

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The use of computational chemistry provides support for the interpretation of experimental studies and allows making predictions about the properties of systems not yet synthesized. Quantum chemistry methods with different levels of electronic structure treatments are more easily found due to computational advances. However, some approximations are still required because of the significant demand for computational resources associated to more advanced methods. Thus, the results obtained may not adequately represent the properties of the systems studied. In the case of compounds containing heavy elements, such as many catalysts, studies that take into account the relativistic effects would be need. Thus, a kinetic study of four reaction categories involving systems containing heavy atoms was conducted. It was noticed that the scalar relativistic effects are generally predominant and that there is not significant differences between the results from the ZORA method in relation to the traditional RECP treatment during the determination of optimized geometries. Nevertheless, the DKH2 calculations failed to describe the geometric parameters of platinum compounds with the same efficiency. On the other hand, it was possible to observe that relativistic effects are very important for a reliable determination of other properties related to chemical kinetics, such as the relative energies along the reaction mechanism. In this case, in addition to scalar relativistic effects, the spin-orbit coupling also becomes crucial for an accurate description of the activation barriers in compounds with elements from the sixth period and beyond. Therefore, a two-step combined treatment is recommended for a correct description of the systems. In general, the geometry optimization step can be performed at the RECP level. However, in order to obtain accurate energy values by relativistic methods, we suggest the use of four-component treatments such as Dirac-Coulomb (DC) and exact two-component formalisms like X2C-MMF.

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Experimental and Theoretical Study of the Kinetics and Mechanism of the Reaction of Chlorine Atoms with CH₃CHClCH₃ and CD₃CDClCD₃

Cited by 4 publications

References 35 publications

Cl Atom Initiated Photo-oxidation of Mono-chlorinated Propanes To Form Carbonyl Compounds: A Kinetic and Mechanistic Approach

Cl Atom Initiated Photo-oxidation of Mono-chlorinated Propanes To Form Carbonyl Compounds: A Kinetic and Mechanistic Approach

Theoretical and experimental studies of the kinetics of the reaction of 1‐chloropropane and fully deuterated 1‐chloropropane with atomic chlorine

Métodos avançados da química quântica relativística aplicados em estudos de cinética química

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