亚硝酸钠 - 维基百科,自由的百科全书
亚硝酸钠 | |||
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识别 | |||
CAS号 | 7632-00-0 | ||
PubChem | 24269 | ||
ChemSpider | 22689 | ||
SMILES |
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InChI |
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InChIKey | LPXPTNMVRIOKMN-REWHXWOFAO | ||
UN编号 | 1500 | ||
EINECS | 231-555-9 | ||
RTECS | RA1225000 | ||
性质 | |||
化学式 | NaNO2 | ||
摩尔质量 | 68.9953 g·mol⁻¹ | ||
外观 | 白色至浅黄色晶体 | ||
密度 | 2.168 g/cm3 | ||
熔点 | 271 °C decomp. | ||
溶解性(水) | 82 g/100 ml (20 °C) | ||
结构 | |||
晶体结构 | 正交晶系 | ||
空间群 | Im2m | ||
晶格常数 | a = 3.5653(8) Å, b = 5.5728(7) Å, c = 5.3846(13) Å [1] | ||
危险性 | |||
警示术语 | R:R8, R25, R50 | ||
安全术语 | S:S1/2, S45, S61 | ||
MSDS | External MSDS | ||
欧盟编号 | 007-010-00-4 | ||
欧盟分类 | 氧化剂 (O) 有毒 (T) 对环境有害 (N) | ||
NFPA 704 | |||
自燃温度 | 489 °C | ||
致死量或浓度: | |||
LD50(中位剂量) | 180 mg/kg (rats, oral) | ||
相关物质 | |||
其他阴离子 | 硝酸钠 | ||
其他阳离子 | 亚硝酸钾 亚硝酸铵 | ||
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。 |
亚硝酸钠(NaNO2)常用于鱼类、肉类等食品的染色和防腐。纯净的亚硝酸钠是一种白色至浅黄色晶体。它有非常好的水溶性和吸湿性,水溶液呈弱碱性,pH约为9,易溶于液氨,微溶于乙醇、甲醇、乙醚等有机溶剂。亚硝酸钠有咸味,被用来制造假的食盐。在空气中,亚硝酸钠会被缓慢氧化成硝酸钠(NaNO3),后者是一种强氧化剂。亚硝酸钠遇有机物易发生爆炸。
亚硝酸钠也被用于以下领域:生产重氮化合物染料、亚硝基化合物和其它有机化合物;纤维纺织品的染色和漂白;照相;作实验室中的抗腐蚀剂;作金属涂层中的添加剂;生产橡胶。它的10%水溶液也被用于电镀。亚硝酸钠同样被用于人或动物的血管扩张、支气管扩张药物中,甚至可以用于氰化物的解毒。
制备
[编辑]
值得注意的是,该反应需要在无氧条件下进行,否则制得的亚硝酸钠很容易被氧化成硝酸钠。
用途
[编辑]日常饮食
[编辑]亚硝酸盐是普通人日常饮食所需的一部分,存在于很多蔬菜中。[2][3][4]在34种蔬菜,包括不同种类的白菜、生菜、菠菜、香菜和萝卜等样品中,亚硝酸盐含量通常在1.1到57 mg/kg之间[5][6]烹饪蔬菜的过程中可能造成硝酸盐的流失,亚硝酸盐的损失却不显著。[6]未经加工的肉类含有0.4-0.5 mg/kg亚硝酸盐和4–7 mg/kg硝酸盐,而腌渍过的肉中含有10–30 mg/kg硝酸盐。[4]亚硝酸盐在动物组织中的代谢产物通常是一种重要的神经递质一氧化氮。[7]一氧化氮最初可以由精氨酸通过一氧化氮合成酶产生或者来源于消化吸收的硝酸盐和亚硝酸盐。[8]早期关于亚硝酸盐对人体负面影响的研究提前使人们认识到一氧化氮在人体代谢中的重要地位,并且知道了人体本身会内源性地产生一氧化氮。
食品添加剂
[编辑]亚硝酸钠作为食品添加剂,不仅可以对鱼类、肉类食品进行染色和保鲜,原理是:亚硝酸盐在酸性条件下分解产生亚硝基( NO ),亚硝基会很快与肌红蛋白反应生成稳定、鲜艳、亮红色的亚硝化肌红蛋白。使肉制品保持稳定的鲜艳红色。因此特别适用于午餐肉、火腿香肠等,而紅燒肉罐头、清炖猪肉罐头、炖肘子等肉制品使用自然色泽,一般不添加亚硝酸钠作为护色剂。亚硝酸钠的INS号是250,因而有些食品标签上写明了使用E250号添加剂,即为亚硝酸钠。
亚硝酸钠还可以抑制肉毒杆菌的生长。后者可以产生肉毒杆菌毒素,造成食物中毒。在欧盟标准下,亚硝酸钠只能以不高于0.6%的含量与食用盐混合使用,它的E编码是E250。对亚硝酸钾的标准与之类似。
用于腌肉时一般和食盐混合。欧洲的腌肉用盐是预先混合好,含0.5–0.9%亚硝酸钠,其余为食盐。美国用的腌肉用盐是叫做“布拉格粉”(Prague Powder),含6.25%亚硝酸钠,其余为食盐,染成粉红色,用前需要再和食盐稀释。[9]中国一般不用这类预拌粉,直接纯品现场稀释。
药用
[编辑]静脉缓慢注射亚硝酸钠现在已经被用于氰化物中毒的急救(参见氰化物#解毒),和硫代硫酸钠配合使用,仅用于严重场合。由于现在有无毒的羟钴胺作为氰化物解药,亚硝酸钠一般只留在急救地点没有羟钴胺时使用。[10]如果同时发生氰化物和一氧化碳中毒且没有羟钴胺用,单用硫代硫酸钠即足够。[11][12]
近期的研究中发现亚硝酸钠对于扩张血管、改善血液循环有显著效果,包括对镰刀型红血球疾病、心肌梗死、脑动脉瘤和肺动脉高压去打等的应用前景,其中一些疾病目前可以导致婴儿死亡。[13][14]但是扩张血管也会造成低血压、头痛、气短等副作用。[15]
化工用途
[编辑]亚硝酸钠被用于胺向重氮化合物的转化,而N2集团具有很好的离去性,生产应用中通过这样的反应来取代氨基。
实验室中,亚硝酸钠也被用于处理过量的叠氮化钠。[16][17]这是因为在酸性条件下,亚硝酸钠与叠氮化钠发生如下反应:
亚硝酸钠被加热到较高的温度(在330 °C以上)后,可以分解产生氧化钠、红棕色的二氧化氮和一氧化氮。[18]
氧化钠可以吸收二氧化碳产生碳酸钠,这有可能避免了一个潜水艇中的船员窒息于高浓度的二氧化碳。[19]
自杀
[编辑]2020和2021年间英语世界报道多起网购亚硝酸钠自杀案例,致使学术著作讨论亚硝酸钠毒性。[20]使用亚硝酸钠作为自杀手段已在Sanctioned Suicide为主的自杀论坛大有讨论。[21]亚硝酸钠也出现在著名的“McCarthy等人诉亚马逊公司”案件中,原告称亚马逊网站的“经常搭配”推薦系統将亚硝酸钠、止吐剂、自杀指南手册搭配成“自杀套装”给健康儿童售卖,属故意辅助自杀。[22]该诉讼于2023年6月被驳回。[23]eBay全网自2019年开始就禁止售卖本品。[24]加拿大已有售卖商以“辅助自杀”罪名被公诉,曾向88位后来死亡的英国人出售本品。[25][26]此外,美国已出台立法,旨在将亚硝酸钠浓度超过10%的产品视为《消费品安全法》禁止的消费品,此举不会影响布拉格粉(浓度6.25%)的销售。[27]
急性毒性
[编辑]这种化合物在含量比较高的状况下它也对包括人的动物表现明显的毒性。亚硝酸钠对鼠的半数致死量为180 mg/kg,对人的已知最低致死量为71 mg/kg,就是说一个重65 kg的人可能被最低4.615g该种物质致死。[28]
怀疑食用亚硝酸钠自杀时,先遣急救員应立刻提供亞甲藍,[29][30][31]治疗大量吞食产生的正鐵血紅蛋白血症。[32]
健康关注
[编辑]过量的亚硝酸钠会致癌。亚硝酸钠在烹调和消化过程中会和食物中的胺反应,产生致癌物质亚硝胺类化合物。传统食品中也存在亚硝胺,例如腌肉和咸鱼干。在19世纪20年代,美国一次重要的肉制品腌渍工艺的改进减少了69%的亚硝酸盐使用,这使得当时胃癌患者的死亡率骤减。[33]而在1970年前后,人们发现抗坏血酸(即维生素C)可以有效抑制亚硝胺的产生。[34]这使得美国要求肉制品中必须含有至少550ppm的抗坏血酸。制造商有时会使用成本更低但效果相当的异抗坏血酸作为替代。制造商也会添加α-生育酚(即维生素E)来起到进一步效果。上述三种化合物均通过它们的抗氧化性来抑制亚硝胺的产生。抗坏血酸为例,它可以通过氧化还原作用将亚硝酸钠的转化物亚硝酸酐还原为一氧化氮,而自身被氧化为脱氢抗坏血酸。[35]
一项最近的研究揭示了长期使用腌渍肉制品与COPD之间的关系。研究者认为这类肉制品中高含量的亚硝酸盐是导致这类肺病的重要因素,但是目前还没有得到理论性的证实。同时这项研究并没有证明亚硝酸盐会提高这类肺病的发病率,而仅仅只是存在某种联系。[36][37]
反应机理
[编辑]致癌物质亚硝胺产生于食物中天然含有的胺类与加工肉制品中亚硝酸盐的化学反应。
- R2NH(胺) + NaNO2(亚硝酸钠)→ R2N-N=O(亚硝胺)
在酸性环境(例如胃液)或中火加热条件(例如烹饪过程)下,亚硝胺可以形成重氮盐。
- R2N-N=O(亚硝胺) +(酸性环境或加热条件)→ R-N2+(重氮盐)
特定的亚硝胺类化合物,例如N-亚硝胺[38]和N-亚硝基四氢吡咯[39]可以产生碳正离子与细胞中的生物亲核试剂发生反应(例如DNA或酶)。
- R-N2+(重氮盐)→ R+(碳正离子) + N2(离去基团) + :Nu(生物亲核试剂)→ R-Nu
一旦这样的亲核取代发生在一个生物大分子上的关键部位,就可能破坏细胞的正常功能,导致细胞癌变或细胞凋亡。
参考文献
[编辑]- ^ T. Gohda, M. Ichikawa. The Refinement of the Structure of Ferroelectric Sodium Nitrite. Journal of the Korean Physical Society. 1996, 29: 551–554.
- ^ Leszczyńska, Teresa; Filipiak-Florkiewicz, Agnieszka; Cieślik, Ewa; Sikora, Elżbieta; Pisulewski, Paweł M. Effects of some processing methods on nitrate and nitrite changes in cruciferous vegetables. Journal of Food Composition and Analysis. 2009-06-01, 22 (4). ISSN 0889-1575. doi:10.1016/j.jfca.2008.10.025 (英语).
- ^ 存档副本. [2011-06-27]. (原始内容存档于2010-04-16).
- ^ 4.0 4.1 Dennis, M. J.; Wilson, L. A. NITRATES AND NITRITES. Caballero, Benjamin (编). Encyclopedia of Food Sciences and Nutrition (Second Edition). Oxford: Academic Press. 2003-01-01: 4136–4141 [2022-11-08]. ISBN 978-0-12-227055-0. doi:10.1016/b0-12-227055-x/00830-0. (原始内容存档于2022-11-08) (英语).
- ^ Correia, Manuela; Barroso, Ângela; Barroso, M. Fátima; Soares, Débora; Oliveira, M. B. P. P.; Delerue-Matos, Cristina. Contribution of different vegetable types to exogenous nitrate and nitrite exposure. Food Chemistry. 2010-06-15, 120 (4). ISSN 0308-8146. doi:10.1016/j.foodchem.2009.11.030 (英语).
- ^ 6.0 6.1 Leszczyńska, Teresa; Filipiak-Florkiewicz, Agnieszka; Cieślik, Ewa; Sikora, Elżbieta; Pisulewski, Paweł M. Effects of some processing methods on nitrate and nitrite changes in cruciferous vegetables. Journal of Food Composition and Analysis. 2009-06-01, 22 (4). ISSN 0889-1575. doi:10.1016/j.jfca.2008.10.025 (英语).
- ^ Meulemans, A.; Delsenne, F. Measurement of nitrite and nitrate levels in biological samples by capillary electrophoresis. Journal of Chromatography B: Biomedical Sciences and Applications. 1994-10-14, 660 (2). ISSN 0378-4347. doi:10.1016/0378-4347(94)00310-6 (英语).
- ^ Southan, G. J.; Srinivasan, A. Nitrogen oxides and hydroxyguanidines: formation of donors of nitric and nitrous oxides and possible relevance to nitrous oxide formation by nitric oxide synthase. Nitric Oxide: Biology and Chemistry. 1998, 2 (4) [2022-11-08]. ISSN 1089-8603. PMID 9851368. doi:10.1006/niox.1998.0187. (原始内容存档于2022-11-18).
- ^ Coudray G. Who poisoned your bacon?. Icon Books. February 2021: xv. ISBN 978-1785786112.
- ^ Streitz MJ, Bebarta VS, Borys DJ, Morgan DL. Patterns of cyanide antidote use since regulatory approval of hydroxocobalamin in the United States. American Journal of Therapeutics. July–August 2014, 21 (4): 244–249. PMID 23689094. S2CID 21116328. doi:10.1097/MJT.0b013e31824ea656.
- ^ Graham J, Traylor J. Cyanide Toxicity. StatPearls. Treasure Island (FL): StatPearls Publishing. 2023 [7 December 2023]. PMID 29939573.
- ^ Baren JM. Pediatric Emergency Medicine. Elsevier Health Sciences. 2008: 1018. ISBN 978-1416000877. (原始内容存档于16 January 2017) –通过Google Books (英语).
- ^ [[美联社|]]. Hot dog preservative could be disease cure. USA Today. 2005-09-05 [2011-06-27]. (原始内容存档于2011-08-07).
- ^ Roxanne Khamsi. Food preservative fights cystic fibrosis complication. NewScientist.com. 27 January 2006 [2011-06-27]. (原始内容存档于2008-09-17).
- ^ World Health Organization. Stuart MC, Kouimtzi M, Hill SR , 编. WHO Model Formulary 2008. World Health Organization. 2009: 65. ISBN 9789241547659. hdl:10665/44053 .
- ^ Sodium Azide. Hazardous Waste Management. [[东北大学 (美国)|]]. March 2003 [2011-06-27]. (原始内容存档于2007-11-04).
- ^ Committee on Prudent Practices for Handling, Storage, and Disposal of Chemicals in Laboratories, Board on Chemical Sciences and Technology, Commission on Physical Sciences, Mathematics, and Applications, National Research Council. Prudent practices in the laboratory: handling and disposal of chemicals. Washington, D.C.: National Academy Press. 1995 [2011-06-27]. ISBN 0309052297. (原始内容存档于2015-03-25).
- ^ 需要注意的是,该反应可逆,故生成的气体会与氧化钠重新化合成亚硝酸钠,因而实验现象并不明显,也不适合实际应用
- ^ Hoshino, Y.; Utsunomiya, T.; Abe, O. ChemInform Abstract: THE THERMAL DECOMPOSITION OF SODIUM NITRATE AND THE EFFECTS OF SEVERAL OXIDES ON THE DECOMPOSITION. Chemischer Informationsdienst. 1981-09-01, 12 (35) [2022-11-08]. S2CID 197241388. doi:10.1002/chin.198135030. (原始内容存档于2022-11-08) (德语).
- ^
- Durão C, Pedrosa F, Dinis-Oliveira RJ. A fatal case by a suicide kit containing sodium nitrite ordered on the internet. Journal of Forensic and Legal Medicine. July 2020, 73: 101989. PMID 32658747. S2CID 219909654. doi:10.1016/j.jflm.2020.101989. hdl:10400.26/34138 .
- Durão C, Pedrosa F, Dinis-Oliveira RJ. Another suicide by sodium nitrite and multiple drugs: an alarming trend for "exit"?. Forensic Science, Medicine, and Pathology. June 2021, 17 (2): 362–366. PMID 33247411. S2CID 227180461. doi:10.1007/s12024-020-00340-2.
- Tomsia M, Głaz M, Nowicka J, Szczepański M. Sodium nitrite detection in costal cartilage and vitreous humor - Case report of fatal poisoning with sodium nitrite. Journal of Forensic and Legal Medicine. July 2021, 81: 102186. PMID 34058704. S2CID 235268052. doi:10.1016/j.jflm.2021.102186.
- McCann SD, Kennedy JM, Tweet MS, Bryant SM. Sodium Nitrite Ingestion: an Emerging Trend in Suicide Attempts Shared via Online Communities. The Journal of Emergency Medicine. March 2021, 60 (3): 409–412. PMID 33712114. S2CID 232218908. doi:10.1016/j.jemermed.2020.10.021.
- Dean DE, Looman KB, Topmiller RG. Fatal methemoglobinemia in three suicidal sodium nitrite poisonings. Journal of Forensic Sciences. July 2021, 66 (4): 1570–1576. PMID 33598944. S2CID 231952466. doi:10.1111/1556-4029.14689.
- Hickey TB, MacNeil JA, Hansmeyer C, Pickup MJ. Fatal methemoglobinemia: A case series highlighting a new trend in intentional sodium nitrite or sodium nitrate ingestion as a method of suicide. Forensic Science International. September 2021, 326: 110907. PMID 34298207. doi:10.1016/j.forsciint.2021.110907.
- Harvey M, Cave G, Chanwai G. Fatal methaemoglobinaemia induced by self-poisoning with sodium nitrite. Emergency Medicine Australasia. October 2010, 22 (5): 463–465. PMID 21040485. S2CID 38780081. doi:10.1111/j.1742-6723.2010.01335.x.
- McCann SD, Tweet MS, Wahl MS. Rising incidence and high mortality in intentional sodium nitrite exposures reported to US poison centers. Clinical Toxicology. December 2021, 59 (12): 1264–1269. PMID 33787434. S2CID 232431594. doi:10.1080/15563650.2021.1905162 .
- Sedhai YR, Atreya A, Basnyat S, Phuyal P, Pokhrel S. The use of sodium nitrite for deliberate self-harm, and the online suicide market: Should we care?. The Medico-Legal Journal. June 2022, 90 (2): 79–80. PMID 33906496. S2CID 233429578. doi:10.1177/0025817221998119.
- Mudan A, Repplinger D, Lebin J, Lewis J, Vohra R, Smollin C. Severe Methemoglobinemia and Death From Intentional Sodium Nitrite Ingestions. The Journal of Emergency Medicine. September 2020, 59 (3): e85–e88. PMID 32713620. S2CID 220797852. doi:10.1016/j.jemermed.2020.06.031.
- ^ Twohey M. Where the Despairing Log On, and Learn Ways to Die. [[纽约时报|]]. 9 December 2021 [24 July 2022].
- ^ Belanger A. Amazon 'suicide kits' have led to teen deaths, according to new lawsuit. Ars Technica. 7 October 2022 [26 August 2023].
- ^ Stempel J. Judge dismisses lawsuit claiming Amazon sold 'suicide kits' to teenagers. Reuters. 28 June 2023 [3 November 2023] (英语).
- ^ Director, eBay (UK) Limited. Re Jason Thompson (deceased) – Sodium Nitrite (PDF). 8 January 2021 [26 August 2023] –通过[[英國司法機構|]].
- ^ Murphy A. Here's why the world will be watching Kenneth Law's court battle. CTV Toronto. 25 July 2023 [26 August 2023].
- ^ Crawford A. 88 UK deaths linked to Canada 'poison seller'. [[英國廣播公司新聞部|]]. 25 August 2023 [26 August 2023].
- ^ Chemical Used in Suicides Faces Sales Ban Under Proposed Law. news.bloomberglaw.com. [3 November 2023] (英语).
- ^ 存档副本. [2011-06-27]. (原始内容存档于2011-12-11).
- ^ Sheehy MH, Way JL. Nitrite intoxication: Protection with methylene blue and oxygen. Toxicology and Applied Pharmacology. 1 November 1974, 30 (2): 221–226. Bibcode:1974ToxAP..30..221S. ISSN 0041-008X. doi:10.1016/0041-008X(74)90093-3.
- ^ Ehlers P, Bryant SM. Immediate methylene blue is critical for sodium nitrite ingestions. The American Journal of Emergency Medicine. June 2023, 68: 186. PMID 37120398. S2CID 258324908. doi:10.1016/j.ajem.2023.04.034.
- ^ Su M, McRae M. 2022 Health Advisory #22 Poisonings and Death Related to Intentional Sodium Nitrite Ingestions (PDF). New York City Department of Health and Mental Hygiene. 8 September 2022 [4 November 2023].
- ^ Lee GW, Lee JB. Antidote for acquired methemoglobinemia: methylene blue. Journal of the Korean Medical Association. 16 December 2013, 56 (12): 1084–1090. doi:10.5124/jkma.2013.56.12.1084 .
- ^ Paik, David C; Saborio, David V; Oropeza, Ruben; Freeman, Harold P. The epidemiological enigma of gastric cancer rates in the US: was grandmother's sausage the cause?. International Journal of Epidemiology. 2001-02, 30 (1) [2022-11-08]. ISSN 1464-3685. S2CID 8474418. doi:10.1093/ije/30.1.181. (原始内容存档于2022-07-14) (英语).
- ^ Mackerness, C.W.; Leach, S.A.; Thompson, M.H.; Hill, M.J. The inhibition of bacterially mediated N -nitrosation by vitamin C: relevance to the inhibition of endogenous N -nitrosation in the achlorhydric stomach. Carcinogenesis. 1989, 10 (2). ISSN 0143-3334. PMID 2492212. doi:10.1093/carcin/10.2.397 (英语).
- ^ Research Newsletter. Linus Pauling Institute. 2014-07-01 [2022-11-08]. (原始内容存档于2015-02-23) (英语).
- ^ Miranda Hitti. Study: Cured Meats, COPD May Be Linked. WebMD Medical News. 17 April 2007 [2011-06-27]. (原始内容存档于2009-04-05).
- ^ Jiang, Rui; Paik, David C.; Hankinson, John L.; Barr, R. Graham. Cured Meat Consumption, Lung Function, and Chronic Obstructive Pulmonary Disease among United States Adults. American Journal of Respiratory and Critical Care Medicine. 2007-04-15, 175 (8) [2022-11-08]. ISSN 1073-449X. PMC 1899290 . PMID 17255565. doi:10.1164/rccm.200607-969OC. (原始内容存档于2022-11-18).
- ^ Najm, Issam; Trussell, R. Rhodes. NDMA Formation in Water and Wastewater. Journal - American Water Works Association. 2001-02, 93 (2). doi:10.1002/j.1551-8833.2001.tb09129.x (英语).
- ^ Bills, Donald D.; Hildrum, Kjell I.; Scanlan, Richard A.; Libbey, Leonard M. Potential precursors of N-nitrosopyrrolidine in bacon and other fried foods. Journal of Agricultural and Food Chemistry. 1973-05, 21 (5) [2022-11-08]. ISSN 0021-8561. PMID 4739004. doi:10.1021/jf60189a029. (原始内容存档于2022-11-08) (英语).
拓展阅读
[编辑]
- Theodore R. Kozlowski, Roger F. Bartholomew. Solvent Properties of Molten NaNO[sub 2] Using a Freezing Point Technique. Journal of The Electrochemical Society. 1967, 114 (9): 937 [2019-04-04]. doi:10.1149/1.2426783 (英语).
外部链接
[编辑]- ATSDR - Case Studies in Environmental Medicine - Nitrate/Nitrite Toxicity(页面存档备份,存于互联网档案馆) U.S. Department of Health and Human Services (public domain)
- International Chemical Safety Card 1120(页面存档备份,存于互联网档案馆).
- European Chemicals Bureau.
- National Center for Home Food Preservation Nitrates and Nitrites.
- TR-495: Toxicology and Carcinogenesis Studies of Sodium Nitrite (CAS NO. 7632-00-0) Drinking Water Studies in F344/N Rats and B6C3F1 Mice.
- FOX news article concerning carcinogicity and hot dogs
- Nitrite in Meat