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Acta Physico-Chimica Sinca  2017, Vol. 33 Issue (8): 1709-1714    DOI: 10.3866/PKU.WHXB201704171
ARTICLE     
Studying ionization and decomposition mechanism of alkyl dinitrites by mass spectrometry
Ling-Xuan WANG,Hua-Tong ZHU,Li-Li ZU*()
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Abstract  

Alkyl dinitrites with two functional groups, R2C(ONO)(CH2)nC(ONO)R2, can easily produce alkoxy radicals and nitric oxide in the atmosphere. Their high activity has led to issues such as photochemical air pollution and the greenhouse effect. Hence, unraveling the decomposition mechanism of alkyl dinitrites is of great significance in understanding their photochemical and thermochemical roles in the atmosphere. In this work, the dissociation process of six alkyl dinitrites was investigated by mass spectrometry under the electron impact energy of 70 eV. Our results indicated that the ruptured fragments had characteristic directivity for the structures of alkyl dinitrites. We detected not only the NO+ fragment ion, due to the common breakage of O-NO bond, but also R2C(ONO)+ resulting from the breakage of α C-C bond in the electron ionization mass spectra. The dissociation mechanism of alkyl dinitrites in which the O-NO or C-C bond directly dissociates is different from photolysis and pyrolysis.



Key wordsAlkyl dinitrites      Mass spectrum      Electron impact      Decomposition mechanism      Gas-phase reaction     
Received: 16 March 2017      Published: 17 April 2017
MSC2000:  O643.1  
Fund:  The project was supported by the National Natural Science Foundation of China(21373033);The project was supported by the National Natural Science Foundation of China(21173024)
Corresponding Authors: Li-Li ZU     E-mail: zull@mail.bnu.edu.cn
Cite this article:

Ling-Xuan WANG,Hua-Tong ZHU,Li-Li ZU. Studying ionization and decomposition mechanism of alkyl dinitrites by mass spectrometry. Acta Physico-Chimica Sinca, 2017, 33(8): 1709-1714.

URL:

http://www.whxb.pku.edu.cn/10.3866/PKU.WHXB201704171     OR     http://www.whxb.pku.edu.cn/Y2017/V33/I8/1709

Fig 1 Total ion chromatograms of six alkyl dinitrites. (a) 1, 2-propyl dinitrite; (b) 2, 3-butyl dinitrite; (c) 1, 3-propyl dinitrite; (d) 1, 2-butyl dinitrite; (e) 1, 4-butyl dinitrite; (f) 1, 5-pentyl dinitrite.
DinitritesRTBPaDiolsBPa
1, 2-propyl dinitrite2.41116.81, 2-propanediol187.2
1, 3-propyl dinitrite2.99125.41, 3-propanediol214.0
2, 3-butyl dinitrite2.88134.72, 3-butanediol185.2
1, 2-butyl dinitrite3.28141.81, 2-butanediol193.6
1, 4-butyl dinitrite4.17148.51, 4-butanediol228.0
1, 5-pentyl dinitrite5.03171.61, 5-pentanediol240.5
Table 1 The retention time (RT, in min) in GC and boiling point (BP, in ℃) of alkyl dinitrites.
Fig 2 EI-MS mass spectra of 1, 2-propyl dinitrite (a), 1, 2-butyl dinitrite (b) and 2, 3-butyl dinitrite (c).
Fig 3 The NBO charge distribution for the neutral (a) and cationic conformer (b) of 1, 2-propyl dinitrite as obtained at the B3LYP/6-311++G(d, p) level.
Mrm/z
(29)
m/z
(30)
m/z
(41)
m/z
(42)
m/z
(43)
m/z
(55)
m/z
(57)
m/z
(60)
m/z
(71)
m/z
(74)
m/z
(85)
m/z
(88)
m/z
(102)
m/z
(116)
m/z
(133)
m/z
(147)
134201000.62.122?7.610?6.1?1.30.1???
148321003.12.25.70.445236.9??7.50.10.3?0.6
148131001.7?520.21.30.23.714??2.5??0.3
148221000.63.4160.710540.12.2?0.32.9?1.2?
148221006.75.47.80.86.8577.60.6?1.1????
16273864631541611100252525?0.2???
Table 2 The molar masses (Mr) of alky dinitrites and the relative abundance of main ions in the mass spectra.
Fig 4 EI-MS Mass spectra of 1, 3-propyl dinitrite(a), 1, 4-butyl dinitrite(b) and 1, 5-pentyl dinitrite(c).
DinitritesAIEVIPCharacter??i
1, 2-propyl dinitrite9.48512.229σONO12.229
1, 2-butyl dinitrite9.38012.195σONO12.195
2, 3-butyl dinitrite9.34412.155σCH3CHONO12.155
1, 3-propyl dinitrite9.76512.277σONO12.277
1, 4-butyl dinitrite9.64512.273σONO12.273
1, 5-pentyl dinitrite9.47712.227σCH2ONO12.227
Table 3 The calculated adiabatic ionization energies (AIE) as obtained at B3LYP/6-311++G(d, p) and vertical ionization potentials (VIP), MO characters and eigenvalues ??i of alkyl dinitrites using OVGF/6-311++G((d, p)).
Fig 5 The NBO charge distribution for the neutral (a) and cationic conformer (b) of 1, 5-pentyl dinitrite as obtained at the B3LYP/6-311++G(d, p) level.
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