二氧化氮 | 10102-44-0

• 分子结构分类: 无机化合物 - 均质非金属化合物 - 其他非金属有机物
• 中文名称: 二氧化氮
• 中文别名: 过氧化氮
• 英文名称: Nitrogen dioxide
• 英文别名: nitric dioxide
• CAS: 10102-44-0
• 化学式: NO₂
• 分子量: 46.0055
• InChiKey: JCXJVPUVTGWSNB-UHFFFAOYSA-N

物化性质

• 物理描述：
  Yellowish-brown liquid or reddish-brown gas (above 70°F) with a pungent, acrid odor.
• 颜色/状态：
  Red to brown gas above 21.1 °C; brown liquid below 21.1 °C; colorless solid at approx -11 °C
• 气味：
  Irritating odor
• 沸点：
  21.15 °C
• 熔点：
  -9.3 °C
• 溶解度：
  Reacts with water (NIOSH, 2016)
• 密度：
  1.448 at 20 °C/4 °C (liquid); 3.3 g/L at 21.3 °C (gas)
• 蒸汽密度：
  1.58 (EPA, 1998) (Relative to Air)
• 蒸汽压力：
  900 mm Hg at 25 °C
• 分解：
  Decomposes at 160 °C. Decomposes (reacts) with water.
• 粘度：
  0.0142 at 26.8 °C (gas): 0.42 CP at 20 °C (liquid)
• 腐蚀性：
  Corrosive to steel when wet, but may be stored in steel cylinders when moisture content is 0.1% or less
• 汽化热：
  9.110 kcal/mole
• 电离电位：
  9.75 eV
• 气味阈值：
  Low odor threshold 2.0 mg/cu m; High odor threshold 10.0 mg/cu m; Irritating concn 20.0 mg/cu m.
• 折光率：
  INDEX OF REFRACTION: 1.40 @ 20 °C
• 稳定性/保质期：

  当温度高于150℃时开始分解，到650℃时完全分解为一氧化氮和氧气。二氧化氮与水反应生成硝酸和一氧化氮；与浓硫酸反应生成亚硝基硫酸；与碱反应生成等摩尔的硝酸盐和亚硝酸盐。在气相状态下，二氧化氮会发生叠合作用，生成四氧化二氮，并且四氧化二氮总是与其保持平衡共存。

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  30.4
• 氢给体数：
  0
• 氢受体数：
  2

ADMET

代谢

经口给予小鼠氨喋呤（AP）和硝酸钠后，吸入二氧化氮（NO2）可导致N-亚硝基二甲胺（NDMA）的生物合成增加，这是通过使用带有热能分析仪检测器的气相色谱分析确定的。这些结果也在大鼠的慢性实验中通过NDMA形成生物标志物系统（肝脏单链DNA损伤、丙氨酸转氨酶、谷胱甘肽-S-转移酶和肝脏S9部分活性）间接得到了证实。通过给予4-甲基吡唑（4-MP）抑制NDMA的代谢，增加了冷冻全小鼠粉末中NDMA生物合成测定的敏感性。结果证实， 可以作为亚硝胺的前体。

Inhalation of nitrogen dioxide (NO2) by mice administered orally amidopyrine (AP) and sodium nitrite resulted in increased biosynthesis of N-nitrosodimethylamine (NDMA), as determined by analysis using gas chromatography with thermal energy analyzer detector. These results were also confirmed indirectly in chronic experiments on rats using the system of biomarkers of NDMA formation (single-stranded DNA liver damages, alanine-aminotransferase, glutathione-S-transferase, and liver S9 fraction activity). The inhibition of NDMA metabolism by 4-methylpyrazol (4-MP) administration increases the sensitivity of NDMA biosynthesis assay in frozen whole-mouse powder. The results confirm that NO2 can serve as the precursor of nitrosamines.

来源:Hazardous Substances Data Bank (HSDB)

代谢

Sprague-Dawley 大鼠在含有低浓度二氧化氮的大气中暴露 24 小时后，在暴露当天及其后的三天内尿液中硝酸盐水平有所增加。作者的研究结果支持了二氧化氮在肺部的主要相互作用是与易于氧化的组织成分反应形成亚硝酸盐，并且他们估计每 ppm 二氧化氮 24 小时暴露在大约形成了 9.6 微摩尔的亚硝酸盐。

Sprague-Dawley rats exposed to atmospheres containing low levels of nitrogen dioxide for 24 hr had increased levels of nitrate in their urine on the day of exposure & on the 3 subsequent days. Authors findings support the hypothesis that the major interaction of nitrogen dioxide in the lung is with readily oxidizable tissue components to form nitrite, & they estimate that 9.6 umol of nitrite is formed in the respiratory tract per ppm nitrogen dioxide 24 hr exposure.

来源:Hazardous Substances Data Bank (HSDB)

代谢

动物吸入二氧化氮后，在其尿液中检出了硝酸盐和亚硝酸盐。

Nitrates and nitrites have been detected in the urine of animals after the inhalation of nitrogen dioxide.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

识别：一氧化氮是一种无色、无味的气体，在水中只有微弱的溶解性。氮氧化物（包括一氧化氮）排放的主要来源是燃烧过程。化石燃料电厂、汽车和家庭燃烧设备排放的氮氧化物，大部分以一氧化氮的形式存在。一氧化氮在环境空气和室内空气中可以存在显著浓度。人类暴露：人类对氮氧化物的暴露程度因室内外、城市与乡村、以及一天中的时间和季节而异。一氧化氮容易被氧化成二氧化氮，然后发生过氧化。由于在一氧化氮暴露中同时存在一些二氧化氮，因此很难区分一氧化氮效应与二氧化氮效应。一氧化氮作为一种细胞内第二信使，调节多种重要酶，并抑制其自身的产生（例如，负反馈）。一氧化氮激活鸟苷酸环化酶，进而增加细胞内cGMP水平。一氧化氮被认为是几个器官系统内的重要内源性第二信使。在特定水平上，吸入的一氧化氮浓度可以在不影响系统循环的情况下引起肺循环的血管舒张。最低有效浓度尚未确定。关于一氧化氮暴露后的肺功能和肺部宿主防御的信息有限，无法得出任何结论。在临床应用中，相对高浓度的 一氧化氮已被短暂使用，没有报告不良反应。动物研究：一氧化氮的毒理学数据库相对于二氧化氮来说较小。在空气中很难获得纯一氧化氮而不受二氧化氮的污染。内源性一氧化氮合成是通过在许多器官系统如神经组织、血管和免疫系统的细胞中，从生理底物形成一氧化氮。一氧化氮可能比二氧化氮更有效地引起肺形态学的某些变化。在一项研究一氧化氮对细菌防御的影响的实验中，在任何研究时间点，两种性别都没有统计学上的显著影响。体外数据显示，一氧化氮刺激鸟苷酸环化酶，导致平滑肌松弛和血管舒张，并对神经系统产生功能影响。这些效应可能是吸入一氧化氮导致肺循环血管舒张和急性支气管扩张剂效应的原因。一氧化氮对血红素结合铁的亲和力是碳 monoxide 的两倍。这种亲和力导致高铁血红蛋白的形成和鸟苷酸环化酶的刺激。此外，一氧化氮与酶中的巯基结合铁反应，最终取代铁。这是一氧化氮细胞毒性的可能机制。一氧化氮可以使DNA脱氨，引发DNA链断裂，并抑制DNA聚合酶和核糖核苷酸还原酶。它可能是抗有丝分裂剂，在大鼠脾细胞中抑制T细胞增殖。

IDENTIFICATION: Nitric oxide is a colorless, odorless gas that is only slightly soluble in water. The main sources of nitrogen oxides (including nitric oxide) emissions are combustion processes. Fossil fuel power stations, motor vehicles and domestic combustion appliances emit nitrogen oxides, mostly in the form of nitric oxide. Nitric oxide can be present at significant concentrations in ambient air and in indoor air. HUMAN EXPOSURE: Human exposure to nitrogen oxides varies from indoors to outdoors, from cities to the countryside, and with the time of day and season. Nitric oxide is readily oxidized to nitrogen dioxide and peroxidation then occurs. Because of the concurrent exposure to some nitrogen dioxide in nitric oxide exposures, it is difficult to discriminate nitric oxide effects from nitrogen dioxide. Nitric oxide functions as an intracellular second messenger modulating a wide variety of essential enzymes, and it inhibits its own production (e.g., negative feedback). Nitric oxide activates guanylate cyclase which in turn increases intracellular cGMP levels. Nitric oxide is acknowledged as an important endogenous second messenger within several organ systems. At certain levels, inhaled nitric oxide concentrations can cause vasodilation in the pulmonary circulation without affecting the systemic circulation. The lowest effective concentration is not established. Information on pulmonary function and lung host defenses consequent to nitric oxide exposure are too limited for any conclusions to be drawn. Relatively high concentrations have been used in clinical applications for brief periods without reported adverse effects. ANIMAL STUDIES: The toxicological database for nitric oxide is small, relative to nitrogen dioxide. It is often difficult to obtain pure nitric oxide in air without some contamination with nitrogen dioxide. Endogenous nitric oxide synthesis occurs by nitric oxide formation from physiological substrate in cells of many of the organ systems such as nerve tissue, blood vessels and the immune system. Nitric oxide may be more potent than nitrogen dioxide in introducing certain changes in lung morphology. In a study examining the effects of nitric oxide on bacterial defenses, there were no statistically significant effects for either sex at any of the time points studied. In vitro data indicate that nitric oxide stimulates guanylate cyclase and leads to smooth muscle relaxation and vasodilation and functional effects on the nervous system. These effects are probably responsible for vasodilation in the pulmonary circulation and an acute bronchodilator effect of inhaled nitric oxide. Nitric oxide has an affinity for heme-bound iron which is two times higher than that of carbon monoxide. This affinity leads to the formation of methemoglobin and the stimulation of guanylate cyclase. Furthermore, nitric oxide reacts with thiol-associated iron in enzymes and eventually displaces the iron. This is a possible mechanism for the cytotoxic effects of nitric oxide. Nitric oxide can deaminate DNA, evoke DNA chain breaks, and inhibit DNA polymerase and ribonucleotide reductase. It might be antimitogenic and inhibit T cell proliferation in rat spleen cells.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

A4；不能归类为人类致癌物。

A4; Not classifiable as a human carcinogen.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 在妊娠和哺乳期间的影响

母乳喂养期间使用总结：目前没有关于在母乳喂养期间将液氮用于皮肤的 临床信息。由于液氮是一种非有毒气体，不太可能出现在母乳中或被婴儿吸收，因此在母乳喂养期间使用被认为是安全的。不需要特别的预防措施。 ◉ 对哺乳婴儿的影响：截至修订日期，没有找到相关的已发布信息。 ◉ 对泌乳和母乳的影响：截至修订日期，没有找到相关的已发布信息。

◉ Summary of Use during Lactation:No information is available on the clinical use of liquid nitrogen on the skin during breastfeeding. Because it is a nontoxic gas that is unlikely to appear in breastmilk or be absorbed by the infant, it is considered safe to use during breastfeeding. No special precautions are required. ◉ Effects in Breastfed Infants:Relevant published information was not found as of the revision date. ◉ Effects on Lactation and Breastmilk:Relevant published information was not found as of the revision date.

来源:Drugs and Lactation Database (LactMed)

毒理性

• 暴露途径

该物质可以通过吸入被身体吸收。

The substance can be absorbed into the body by inhalation.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

毒理性

• 暴露途径

吸入，吞食，皮肤和/或眼睛接触

inhalation, ingestion, skin and/or eye contact

来源:The National Institute for Occupational Safety and Health (NIOSH)

吸收、分配和排泄

一些报告表明，二氧化氮被肺吸收并和血液发生反应... 氮气烟雾主要作用于肺泡壁。

Several reports suggest that nitrogen dioxide is absorbed in lungs and reacts with blood ... Nitrous fumes ... act chiefly on alveolar walls.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

50到60%的二氧化氮在恒河猴静息呼吸时被保留，气体分布在整个肺部。一旦被吸收，二氧化氮或化学中间体在停止暴露后会在肺部停留很长时间，并且通过血流传播到肺外部位。

50 to 60% of inspired nitrogen dioxide in rhesus monkeys was retained during quiet resp, the gas was distributed throughout lungs. Once absorbed, nitrogen dioxide or chem intermediates remained within lungs for prolonged periods after cessation of exposure, & dissemination to extrapulmonary sites occurred via blood stream.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

在大约50%的二氧化氮通过兔子的鼻子和喉咙时被吸收。50到60%的二氧化氮被暴露在0.3到0.9 ppm二氧化氮环境中的猴子吸收。使用的放射性示踪剂在肺中停留了很长时间，并且有一些扩散到其他组织。

... Found that about 50% of nitrogen dioxide was absorbed in passage through the nose and throat of a rabbit. ... 50 to 60% of nitrogen dioxide was absorbed by monkeys exposed to 0.3 to 0.9 ppm of nitrogen dioxide. The radioactive tracer ... used remained in the lung for prolonged periods, with some spread to other tissues.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

二氧化氮在上呼吸道的粘液中部分溶解，但它也相对均匀地分布在整个呼吸道中；它通过循环系统在体内进一步传播。

Nitrogen dioxide is partly dissolved in the mucus of the upper airways, but it is also fairly evenly distributed throughout the respiratory tract; it is furthur spread in the body by the circulatory system.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 危险等级：
  2.3
• 危险品标志：
  T+
• 安全说明：
  S26,S28,S36,S36/37/39,S45,S9
• 危险类别码：
  R26,R34
• WGK Germany：
  1
• RTECS号：
  QX1575000
• 危险类别：
  2.3
• 危险标志：
  GHS03,GHS04,GHS05,GHS06
• 危险品运输编号：
  UN 1067 2.3
• 危险性描述：
  H270,H314,H330,H412
• 危险性防范说明：
  P220,P244,P260,P280,P304 + P340 + P310,P305 + P351 + P338
• 储存条件：
  库房应保持通风、低温和干燥，并与其他易燃或可燃物品分开存放。

SDS

第一部分：化学品名称

制备方法与用途

制备方法

精馏法以直接法制备浓硝酸时所用液体四氧化二氮为原料，经过精馏塔精馏、冷凝器冷凝后，即可获得液体四氧化二氮。

用途简介

二氧化氮是氨氧化制取硝酸过程中的中间产物。

用途

二氧化氮同样是氨氧化制取硝酸的中间产物。

反应信息

• 作为反应物：
  描述：

  二氧化氮 在 phenol 作用下， 以 苯 为溶剂， 生成 2,4-二硝基酚
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: N: MVol.3, 4.6, page 803 - 817

  摘要：

  DOI：
• 作为产物：
  描述：

  亚硝酰氯 生成 二氧化氮
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: N: MVol.3, 4.2, page 757 - 764

  摘要：

  DOI：
• 作为试剂：
  描述：

  bis (2-chloroethyl) sulphide 在 二氧化氮 、 Petroleum ether 作用下， 生成 氮芥亚砜
  参考文献：
  名称：

  DE335601

  摘要：

  公开号：

文献信息

• Pentafluoronitrosulfane, SF₅NO₂
  作者：Norman Lu、Joseph S. Thrasher、Stefan von Ahsen、Helge Willner、Drahomir Hnyk、Heinz Oberhammer

  DOI：10.1021/ic0516212

  日期：2006.2.1

  The synthesis of pentafluoronitrosulfane, SF5NO2, is accomplished either by reacting N(SF5)3 with NO2 or by the photolysis of a SF5Br/NO2 mixture using diazo lamps. The product is purified by treatment with CsF and repeated trap-to-trap condensation. The solid compound melts at -78 degrees C, and the extrapolated boiling point is 9 degrees C. SF5NO2 is characterized by 19F, 15N NMR, IR, Raman, and

  通过使N（SF5）3与NO2反应或通过使用重氮灯对SF5Br / 混合物进行光解来完成五氟硝基硫烷SF5 的合成。该产物通过用CsF处理和重复的阱至阱冷凝来纯化。固体化合物在-78摄氏度下熔化，外推沸点为9摄氏度。SF5 的特征在于19F，15N NMR，IR，拉曼光谱和UV光谱以及质谱。SF5 的分子结构通过气体电子衍射确定。该分子具有C2v对称性，其中 基团错开赤道SF键和一个非常长的1.903（7）埃SN键。计算的键焓在很大程度上取决于计算方法：159（MP2 / 6-311G ++（3df））和87 kJ mol（-1）（B3LYP / 6-311 ++ G（3df））。
• Enhanced Formation of Ozone by the Addition of Chloropicrin (Trichloronitromethane) to Propene/NO/Air/Photoirradiation Systems
  作者：Shiro Hatakeyama、Takashi Imamura、Nobuaki Washida

  DOI：10.1246/bcsj.72.1497

  日期：1999.7

  chloropicrin in air at 1 atm was performed in a 6-m3 photochemical reaction chamber with a combination of Xe arc lamps and Pyrex filters as a light source. Phosgene was obtained as one of the main products with a yield of unity. No nitrosyl chloride was observed, which supports the C–N scission mechanism for the photolysis. Photochemical ozone formation was enhanced when chloropicrin was added to the

  氯化苦在空气中在 1 个大气压下的光解是在 6 立方米的光化学反应室中进行的，该反应室结合了氙弧灯和耐热玻璃过滤器作为光源。光气作为主要产品之一获得，收率一致。没有观察到亚硝酰氯，这支持光解的 C-N 断裂机制。在达到臭氧浓度最大值后，将氯化苦加入丙烯/NO/空气/光辐照系统时，光化学臭氧的形成得到增强。然而，在所采用的条件下，氯化苦的臭氧形成因子估计为每摩尔分解的氯化苦形成 0.25 摩尔的臭氧。这意味着 Cl 原子本身有助于破坏臭氧，而不是在实验条件下形成臭氧。氯化苦释放的 NO2 是臭氧增强的来源。如果氯化苦作为土壤熏蒸剂的用量增加，会导致土壤中臭氧浓度升高。...
• The Structure of Active Sites in Me–V–O Catalysts (Me = Mg, Zn, Pb) and Its Influence on the Catalytic Performance in the Oxidative Dehydrogenation (ODH) of Propane
  作者：P Rybarczyk、H Berndt、J Radnik、M.-M Pohl、O Buyevskaya、M Baerns、A Brückner

  DOI：10.1006/jcat.2001.3251

  日期：2001.8

  Me–V–O catalysts (Me = Mg, Zn, Pb) of different Me : V ratios were characterized with respect to phase composition, structure and valence state of vanadium sites as well as composition and acid–base properties of the surface using XRD, TEM, TPR, TPD/TPRS, FTIR, potentiometric titration, XPS, EPR, and UV/VIS-DRS. The latter two techniques were also applied in situ under catalytic reaction conditions

  使用X射线衍射分析了不同Me：V比的Me –V–O催化剂（Me = Mg，Zn，Pb）相对于钒部位的相组成，结构和价态以及表面的组成和酸碱性质，TEM，TPR，TPD / TPRS，FTIR，电位滴定，XPS，EPR和UV / VIS-DRS。后两种技术也在催化反应条件下原位应用。通过比较催化剂的表征结果和催化测试的结果，得出以下结构反应性关系：V 5+和V 4+均催化丙烷的ODH。然而，V 4+似乎比V 5+更具选择性，但活性更高。与VO 4四面体相比，八面体或方形锥体配位的V位更活跃，但选择性更低。分别存在于晶体金属原酸盐和丙酮酸盐中的分离的VO 4和V 2 O 7单元比无定形簇甚至晶体链或层状结构中的VO x物种更具选择性，但活性较低。由不同金属阳离子引起的催化性能差异不仅受金属阳离子的氧化电势控制，而且在很大程度上受酸碱性能，晶体尺寸和结构紊乱程度的影响。Me的催化活性和选择性–V–O催化剂按Mg>
• Dinitrogen Tetraoxide Complexes of Iron(III) and Copper(II) Nitrates as Versatile Reagents for Organic Syntheses. Efficient Oxidative Deprotection of Silyl or Tetrahydropyranyl Ethers, Acetals, and Thioacetals
  作者：Habib Firouzabadi、Nasser Iranpoor、Mohammad Ali Zolfigol

  DOI：10.1246/bcsj.71.2169

  日期：1998.9

  efficiently in the absence of solvents at room temperature. Over-oxidation of the products has not been observed in these reactions. A synergic effect of N2O4 upon the oxidation abilities of metal nitrates is observed.

  Fe(NO3)3·1.5 和Cu( )2·N2O4 是各种甲硅烷基和四氢吡喃基醚、缩醛和硫缩醛在非质子有机溶剂中氧化脱保护的有效试剂。Fe( )3·1.5 也能够在没有溶剂的情况下在室温下有效地进行反应。在这些反应中没有观察到产物的过度氧化。观察到 对金属硝酸盐氧化能力的协同作用。
• The Formation of Methyl Isocyanate during the Reaction of Nitroethane over Cu-MFI under Hydrocarbon-Selective Catalytic Reduction Conditions
  作者：Irene O.Y Liu、Noel W Cant、Brian S Haynes、Peter F Nelson

  DOI：10.1006/jcat.2001.3343

  日期：2001.10

  deposited material as demonstrated by the temperature–programmed decomposition in helium. The main reaction pathway with the two nitrocompounds appears to be rearrangement followed by dehydration to the corresponding isocyanate and hydrolysis to amine (or ammonia), with the latter steps proceeding on Brønsted acid sites. Nitrogen is then formed by reaction with NO/O2 on the transition metal as in the

  在Cu-MFI上研究了O 2存在下硝基乙烷与NO的反应。对于短时间的在线运行，在250°C以上以CO 2和N 2为产物即可完成转化。但是，在低于330°C的温度下，沉积物的积聚会导致异氰酸酯和CO的出现而导致失活。FTIR气体分析证实了有毒异氰酸甲酯（CH 3 NCO）的形成，产率接近25％，异氰酸含量更小（HNCO）。硝基甲烷的反应类似，但失活仅使HNCO慢一个数量级。HNCO的出现伴随着大量的HCN和NH 3。硝基乙烷在O 2中反应以类似于NO / O 2的方式单独使用，但其初始N 2产率不到一半。失活速度更快，少量的HCN和NH 3与CH 3 NCO和HNCO同时出现。在硝基乙烷系统中，HNCO，HCN和NH 3由沉积材料的分解产生，如氦气中的程序升温分解所证明的那样。与这两种硝基化合物的主要反应途径似乎是重排，然后脱水为相应的异氰酸酯，然后水解为胺（或氨），随后的步骤在布朗斯台德酸位进行。然后通过与NO

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