完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.author | Raghunath, Putikam | en_US |
dc.contributor.author | Lin, M. C. | en_US |
dc.date.accessioned | 2019-04-02T05:59:50Z | - |
dc.date.available | 2019-04-02T05:59:50Z | - |
dc.date.issued | 2018-10-18 | en_US |
dc.identifier.issn | 1932-7447 | en_US |
dc.identifier.uri | http://dx.doi.org/10.1021/acs.jpcc.8b07030 | en_US |
dc.identifier.uri | http://hdl.handle.net/11536/148354 | - |
dc.description.abstract | The mechanism responsible for the explosion of solid mixtures of nitrogen tetroxide (N2O4) and hydrazine (HZ) or methyl-substituted HZs, detected experimentally by slow warming from 77 to 203-223 K, has been elucidated by quantum chemical calculations using the Vienna ab initio simulation package code. The result of the calculation for the reaction of a N2O4 molecule embedded in the middle of the N2H4 molecular crystal, N2O4@HZ(23), indicates that a loose nonconventional transition state (TS) occurring by stretching the O2N-NO2 bond up to 2.18 A with the concerted rotation of one of the NO2 groups producing the reactive ONONO2 isomer (ONONO2@HZ(23)) has a low 13.1 kcal/mol barrier at TS1; the process is exothermic by 45 kcal/mol, reflecting the much stronger ONONO2 binding with N2H4. A further simultaneous reaction of ONONO2 with 2N(2)H(4) in the same unit cell occurs with a small 1.4 kcal/mol barrier producing NO3- + NH2N(H)NO + N2H5+ with an overall exothermicity of 70.2 kcal/mol. The mechanism for this last-step reaction is distinctly different from that in the gas phase taking place via a five-centered concert mechanism giving N2H3NO and HNO3, which can further produce N2H5+NO3- by the rapid acid-base neutralization process. On the basis of the predicted structure, energy, and vibrational frequencies at TS1, we estimated the rate constant at 218 K for the N2O4-ONONO2 isomerization reaction in solid N2H4 to be 1.35 s(-1), giving the half-life of N2O4 @HZ 23 to be as short as 0.5 s. This result can explain why the slow warming of the solid mixtures of N2O4 and N2H4 from 77 K exploded reproducibly at 218 K. | en_US |
dc.language.iso | en_US | en_US |
dc.title | Isomerization of N2O4 in Solid N2H4 and Its Implication for the Explosion of N2O4-N2H4 Solid Mixtures | en_US |
dc.type | Article | en_US |
dc.identifier.doi | 10.1021/acs.jpcc.8b07030 | en_US |
dc.identifier.journal | JOURNAL OF PHYSICAL CHEMISTRY C | en_US |
dc.citation.volume | 122 | en_US |
dc.citation.spage | 23501 | en_US |
dc.citation.epage | 23505 | en_US |
dc.contributor.department | 交大名義發表 | zh_TW |
dc.contributor.department | National Chiao Tung University | en_US |
dc.identifier.wosnumber | WOS:000448087900029 | en_US |
dc.citation.woscount | 0 | en_US |
顯示於類別: | 期刊論文 |