Mechanism and Kinetics on the Reaction of Isopropyl Nitrate with Cl， OH and NO3 Radicals

doi:10.7503/cjcu20210591

Abstract

Abstract:

The reaction mechanism of （CH₃）₂CHONO₂ with X（X=Cl， OH and NO₃ radical） was studied at M06-2X/ 6-311++G（d，p） level of theory， and the energy of the stationary points was calculated by CCSD（T） method. The kinetics of the reaction was calculated by the conventional transition state theory. The hydrogen bonded complexes are formed firstly by isopropyl nitrate and X radical， and X radical can abstract the α-H or β-H atoms from （CH₃）₂CHONO₂. The α-H abstraction is the main channel， and the main products are （CH₃）₂CO + NO₂ + HCl（H₂O or HNO₃）. The yield of α-H abstraction products decreases as the temperature increases from 200 K to 500 K for IPN + OH reaction. The overall rate constant for the reaction of （CH₃）₂CHONO₂ with Cl atom， OH and NO₃ radical at 300 K is 3.933×10^-11， 1.182×10^-13， and 7.134×10^-19 cm³·molecule^-1·s^-1， respectively. The theoretical kinetics data is in consistent with the previous experimental values for the reaction of OH with isopropyl nitrate.

Key words: Isopropyl nitrate, Radical, Reaction mechanism, Kinetics

CLC Number:

O641

TrendMD:

SUN Cuihong, LYU Liqiang, LIU Ying, WANG Yan, YANG Jing, ZHANG Shaowen. Mechanism and Kinetics on the Reaction of Isopropyl Nitrate with Cl， OH and NO₃ Radicals[J]. Chem. J. Chinese Universities, 2022, 43(2): 20210591.

Figures/Tables 6

Fig.1 Molecular graphs of hydrogen abstraction reaction complexesThe small red sphere denotes the bond critical point between two atoms.

Fig.2 Geometries of hydrogen abstraction transition statesThe unit of the interatomic distances are given in nm.

Fig.3 Potential energy surfaces(including zero?point corrections) of the IPN + X reaction(A) IPN+Cl; (B) IPN+OH; (C) IPN+NO3.

Table 1 Rate constants(k) of the β-H abstraction channel at 300 K

Reaction	k/（cm³·molecule^-1·s^-1）
Reaction	IPN + Cl	IPN + OH	IPN + NO₃
absH₁	4.023×10^-15	1.001×10^-15	1.29×10^-21
absH₂	4.172×10^-15	1.318×10^-15	2.38×10^-22
absH₃	2.330×10^-15	2.223×10^-16	1.35×10^-22
absH_1′	4.050×10^-15	7.012×10^-16	9.03×10^-22
absH_2′	3.154×10^-15	1.424×10^-15	1.09×10^-22
absH_3′	5.303×10^-15	3.519×10^-16	2.59×10^-45
absH_β	2.303×10^-14	5.019×10^-15	2.673×10^-21
absH_α	3.930×10^-11	1.132×10^-13	7.107×10^-19
absH_α + absH_β	3.933×10^-11	1.182×10^-13	7.134×10^-19

Fig.4 Rate constants(k) in 200—500 K(A) IPN + Cl; (B) IPN + OH; (C) IPN + NO3.

Fig.5 Branching ratios of the α?H and β?H abstraction for the IPN + OH reaction

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Mechanism and Kinetics on the Reaction of Isopropyl Nitrate with Cl， OH and NO₃ Radicals

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