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Products and Mechanistic Investigations on the Reactions of Hydrazines with Ozone in Gas-Phase

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Products and Mechanistic Investigations on the Reactions of Hydrazines with Ozone in Gas-Phase S S symmetry Article Products and Mechanistic Investigations on the Reactions of Hydrazines with Ozone in Gas-Phase Dan Huang 1, Xiangxuan Liu 1, Zheng Xie 1,* , Xuanjun Wang 1, Xin Gao 2 and Yuxue Yang 1 1 High-Tech Institute of Xi’an, Xi’an 710025, China; [email protected] (D.H.); [email protected] (X.L.); [email protected] (X.W.); [email protected] (Y.Y.) 2 High-Tech Institute of Beijing, Beijing 10085, China; [email protected] * Correspondence: [email protected] Received: 30 July 2018; Accepted: 6 September 2018; Published: 11 September 2018 Abstract: The toxic transformation products of hydrazines are of great concern. These products’ properties combined with their formation mechanisms are needed to assess their potential environmental and human impacts. In this study, the gas-phase reaction of hydrazine (N2H4), monomethyldrazine (MMH) and unsymmetrical dimethyhydrazine (UDMH) with O3 have been studied at varying reactant ratios, both in the presence and absence of a radical trap. Gas chromatography-mass spectroscopy (GC-MS) has been implied to follow reactant consumption and product formation. Apart from the reported products detected by Fourier transform infrared spectroscopy (FT-IR), the newly found compounds (hydrazones, formamides, dimethylamine, 1,1,4,4-tetramethyl-1,2-tetrazene,dimethylamino-acetonitrile, N2,H2O, et al.) are identified by GC-MS. The relative yields of the organic products vary considerably at different O3/MMH or UDMH ratios. UDMH and MMH are confirmed as high potential precursors of N-nitrosodimethylamine (NDMA). The presence of hydroxyl radicals (HO·) hinders NDMA formation in MMH-O3 system. Meanwhile, it increases NDMA formation in UDMH-O3 system. The suggested reaction mechanisms which account for the observed products are discussed. Keywords: hydrazines; ozone; products; mechanism 1. Introduction Hydrazine (N2H4) and its alkyl derivatives, monomethyldrazine (MMH) and unsymmetrical dimethylhydrazine (UDMH) have been the main high-energy fuels for rocket launching for decades. Considering these compounds are used in large quantity every year, the releases to the atmosphere stemming from storage, transportation and filling cannot be ignored [1]. The hydrazines themselves are hazards to humans. The American Conference of Governmental Industrial Hygienist (ACGIH) has recommended that the threshold limit values (TLVs) for N2H4, MMH, and UDMH be lowered from 100, 200 and 500 ppb, respectively, to 10 ppb in air [2,3]. A major concern is that the toxicity of considerable amounts of the huge list of transformation products are equal to or greater than that of the hydrazines themselves [4,5]. N-nitrosodimethylamine (NDMA) can be taken as an example, whose theoretical cancer risk level is 0.7 ng/m3 in air [6]. In order to explore the atmospheric fate of these chemicals, lots of studies have been done to obtain chemical properties and formation mechanism of transformation products. Since the hydrazines cannot be photolyzed in the solar actinic region (l > 290 nm), their likely reaction pathways in the atmosphere are reaction with ozone and hydroxyl radical. In the 1980’s, The rate constants for the reactions of hydroxyl radical, ozone with all three of the hydrazines have been measured by the Statewide Air pollution Reasearch Center (SAPRC) of the University of California at Riverside [7]. The results show that all three of the hydrazines could be rapidly consumed by Symmetry 2018, 10, 394; doi:10.3390/sym10090394 www.mdpi.com/journal/symmetry Symmetry 2018, 10, 394 2 of 13 Symmetry 2018, 10, x FOR PEER REVIEW 2 of 13 reactionsreactions with with ozone ozone as wellas well as by as reactions by reactions with hydroxylwith hydroxyl radicals radicals [8]. The [8]. specific The specific ozonation ozonation products observedproducts in observed this laboratory in this are laboratory H2O2 and are N2 OH2 fromO2 and N2 HN42;O methyl from N hydroperoxide,2H4; methyl hydroperoxide, methyldiazene, diazomethane,methyldiazene, HCHO, diazomethane, CH3OH fromHCHO, MMH; CH3OH NDMA from inMMH; large NDMA yields fromin large UDMH yields [9 from]. The UDMH reaction of[9].The UDMH reaction with ozoneof UDMH is of with great ozone interest is of great because interest itleads because to it a leads high to yields a high of yields NDMA of NDMA [10–12 ]. The[10–12]. NDMA The formation NDMA mechanismformation mechanism from UDMH from ozonation UDMH ozonation has been has investigated been investigated by theoretical by calculationstheoretical [ 13calculations,14]. The NDMA[13,14]. The formation NDMA pathways formation includepathways hydrogen include hydrogen atom abstraction atom abstraction and direct oxygenand direct atom additionoxygen atom [15]. Theaddition results [15]. also The indicate results that also HO indicate· plays that a key HO· role plays in promoting a key role NDMA in formation.promoting However, NDMA theformation. experiment However, shows the that experime the radicalnt shows traps that increase the radical the NDMA traps formationincrease the [11 ]. Furthermore,NDMA formation various [11]. analytical Furthermore, techniques various such analytical as high techniques performance such liquid as high chromatography-mass performance liquid spectroscopychromatography-mass (HPLC-MS) spectroscopy[16–18], gas chromatography-mass (HPLC-MS) [16–18], gas spectroscopy chromatography-mass (GC-MS) [3,19 spectroscopy,20], and solid phase(GC-MS) micro-extraction [3,19,20], and (SPME-GC/MS) solid phase micro-extraction [21] have been (SPME-GC/MS) used for the identification [21] have been and used quantitative for the determinationidentificationof and these quantitative transformation determination products, of these and moretransformation than 30 oxidative products, productsand morehave than been30 identified.oxidative However,products thehave information been identified. about Howeve the productsr, the ofinformation the hydrazines about reactionthe products with ozoneof the is scarce,hydrazines and the reaction HO· influence with ozone on is NDMAscarce, and formation the HO· mechanisminfluence on isNDMA still in formation discussion. mechanism In order is to still in discussion. In order to find more products and more deeply understand the mechanism of the find more products and more deeply understand the mechanism of the hydrazines reaction with hydrazines reaction with ozone, GC-MS is utilized to follow reactant consumption and product ozone, GC-MS is utilized to follow reactant consumption and product formation. The reactions of formation. The reactions of N2H4, MMH, and UDMH with O3 are investigated at varying reactant N H , MMH, and UDMH with O are investigated at varying reactant ratios, both in the presence 2ratios,4 both in the presence and absence3 of radical traps. Meanwhile, the information of the highest and absence of radical traps. Meanwhile, the information of the highest occupied molecular orbital occupied molecular orbital (HOMO) has been found to account for the possible attack sites of N2H4, (HOMO)MMH, UDMH has been by found ozone. to Moreover, account forthe theformation possible mech attackanisms sites of ofthe N major2H4, MMH,detected UDMH products by have ozone. Moreover,been discussed. the formation mechanisms of the major detected products have been discussed. 2. Experimental Section 2. Experimental Section 2.1. Reaction Chamber and GC-MS System 2.1. Reaction Chamber and GC-MS System TheThe experiments experiments werewere carried out out using using a chambe a chamberr (internal (internal volume volume of 500 of mL, 500 cylinder). mL, cylinder). The Thedetailed detailed schematic schematic diagram diagram of this of this apparatus apparatus is provided is provided in Figure in Figure 1. 1. Six-way vavle GC/MS N2 Reaction Chamber Ozonier Ethanol FigureFigure 1. 1.Schematic Schematicdiagram diagram ofof the main experimental apparatus. apparatus. 2.2.2.2. Materials Materials AnhydrousAnhydrous hydrazine hydrazine (stated (stated purity purity 97+%,97+%, HenanHenan Liming Liming Chemical Chemical Reagent Reagent Co., Co., Zhengzhou, Zhengzhou, China),China), methylhydrazine methylhydrazine (98%, (98%, HenanHenan LimingLiming Chemical Reagent Reagent Co., Co., China.), China), and and unsymmetrical unsymmetrical dimethylhydrazinedimethylhydrazine (99+%, (99+%, Henan Henan LimingLiming Chemical Reagent Reagent Co., Co., China.) China) were were commercial commercial available. available. OzoneOzone was was produced produced in in a a laboratory laboratory ozonizer ozonizer withwith oxygen source source (Model (Model FL-810ET, FL-810ET, Shenzhen Shenzhen Feili Feili ElectricElectric Technology Technology Co., Co., Shenzhen, Shenzhen, China). China). SymmetrySymmetry2018 2018, 10, 10, 394, x FOR PEER REVIEW 33 of of 13 13 2.3. Products Analysis 2.3. Products Analysis Before each runs, the reaction chamber was flushed with the pure N2. The blanked sample was Before each runs, the reaction chamber was flushed with the pure N . The blanked sample was analyzed to make sure that the gas in the reaction chamber was pure. Then2 the reaction chamber (500 analyzed to make sure that the gas in the reaction chamber was pure. Then the reaction chamber mL, cylinder) was evacuated. The samples (N2H4 10μL, MMH 10μL, UDMH 10μL) were injected (500 mL, cylinder) was evacuated. The samples (N H 10 µL, MMH 10 µL, UDMH 10 µL) were injected into it. After 5 min, the chamber was flushed with2 4 different concentration ozone until the pressure into it. After 5 min, the chamber was flushed with different concentration
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