一氧化二氯

一氧化二氯
识别
CAS号	7791-21-1
PubChem	24646
ChemSpider	23048
SMILES	ClOCl;
InChI	1/Cl2O/c1-3-2;
InChIKey	RCJVRSBWZCNNQT-UHFFFAOYAA
ChEBI	30198
性质
化学式	Cl2O
摩尔质量	86.91 g·mol−1
外观	棕黄色气体
密度	2.089 g/cm3（90 K，-183 °C）
熔点	−120.6 °C
沸点	2.0 °C
溶解性（水）	143.6 g/100 ml，缓慢水解
溶解性	可溶于四氯化碳
结构
偶极矩	0.78 ± 0.08 D
热力学
ΔfHm⦵298K	+80.3 kJ mol−1
S⦵298K	265.9 J K−1 mol−1
危险性
MSDS
	GHS危险性符号;
GHS提示词	DANGER
H-术语	H290, H314, H400, H411
P-术语	P234, P260, P264, P273, P280, P301+330+331, P303+361+353, P304+340, P305+351+338, P310, P311, P321, P363, P390
NFPA 704	4 3 3
相关物质
其他阳离子	水; 二氟化氧; 一氧化二溴; 一氧化二碘
相关氯的氧化物	七氧化二氯; 二氧化氯
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

一氧化二氯是氯的氧化物之一，也是次氯酸的酸酐，化学式为Cl₂O。它在1834年由安托万·巴拉尔（英语：Antoine Jérôme Balard）首次合成，^[4]之后盖-吕萨克确定了其化学组成。在室温下，一氧化二氯是可溶于水和有机溶剂的棕黄色气体，在液态下呈红棕色，在固态下则变成樱桃红色^[1]。它是强氧化剂和氯化剂。

Quick Facts 一氧化二氯, 识别 ...

Close

制备

一氧化二氯最早的制备方法是使氯气和氧化汞反应而成，^[5]但此法成本昂贵，且因有汞中毒的风险而非常危险。

2 Cl₂ + HgO → HgCl₂ + Cl₂O

一个较为安全方便的制备方法是使氯气和湿润的碳酸钠在20–30 °C下反应：^[5]

2 Cl₂ + 2 Na₂CO₃ + H₂O → Cl₂O + 2 NaHCO₃ + 2 NaCl

2 Cl₂ + 2 NaHCO₃ → Cl₂O + 2 CO₂ + 2 NaCl + H₂O

氯气和无水碳酸钠也能反应，但需将反应温度提高到150–250 °C。由于一氧化二氯在高温下不稳定，^[6]因此需要不断从反应体系中移去产物一氧化二氯来避免分解。

2 Cl₂ + Na₂CO₃ → Cl₂O + CO₂ + 2 NaCl

结构

一氧化二氯的结构与水和次氯酸相似，都是角形分子。它的Cl-O键长为170.0 pm，Cl-O-Cl键角为110.9°。^[7]这个比水和次氯酸大的键角是两个氯原子的位阻效应导致的。

固态的一氧化二氯呈四方晶系，空间群 I4₁/amd，与冰VIII同构。^[8]

反应

和无机化合物的反应

一氧化二氯易溶于水，^[9]并与HOCl达成平衡。

2 HOCl ⇌ Cl₂O + H₂O K (0 °C) = 3.55x10⁻³ dm³/mol

虽然一氧化二氯在平衡中处于劣势，但它才是饮水氯化中的活性物质。^[10]

一氧化二氯可和金属卤化物反应，产生氯氧化物并放出Cl₂。^[11]^[12]^[5]

VOCl₃ + Cl₂O → VO₂Cl + 2 Cl₂

TiCl₄ + Cl₂O → TiOCl₂ + 2 Cl₂

SbCl₅ + 2 Cl₂O → SbO₂Cl + 4 Cl₂

某些非金属卤化物也可以参与类似的反应。^[13]^[14]

AsCl₃ + 2 Cl₂O → AsO₂Cl + 3 Cl₂

NOCl + Cl₂O → NO₂Cl + Cl₂

它和五氧化二氮反应，得到硝酸氯（ClNO₃），^[15]和三氟氧化氯反应则可以得到一氟化氯和氯酰氟。^[16]一氧化二氯和氨的反应会爆炸，生成氮气、氯气和水。^[1]

一氧化二氯与碱金属和碱土金属的氢氧化物溶液反应生成相应的次氯酸盐^[1]，而干燥的次氯酸盐可被一氧化二氯进一步氧化成氯酸盐。^[1]

和有机化合物的反应

一氧化二氯是有效的氯化剂，可以把芳香化合物的侧链氯化^[17]，而和酚或芳香醚的反应则主要氯化芳香环。^[18]它和醇反应会生成次氯酸酯，如和叔丁醇反应生成次氯酸叔丁酯。^[19]一氧化二氯也是次氯酸和烯烃或芳香化合物的反应中的活性物质。^[20]^[21]

光化学反应

一氧化二氯见光分解，产生O₂和Cl₂。这个反应是自由基反应，闪光光解（英语：flash photolysis）表明一氧化氯（ClO·）是反应的主要中间体。^[22]

2 Cl₂O → 2 Cl₂ + O₂

爆炸性

一氧化二氯会爆炸，但对它的研究不充分。一氧化二氯的爆炸下限很高，达到23.5%，即它和氧气在室温下的混合物需要含有至少23.5% Cl₂O才能被电火花引爆。^[23]有研究称一氧化二氯在强光下会爆炸，但此研究有争议。^[24]^[25]将一氧化二氯迅速加热或缓慢加热到120 °C都会使它爆炸。^[5]液态一氧化二氯对冲击敏感。^[26]

用处

一氧化二氯是生产次氯酸钙、氯代溶剂和氯代异氰尿酸盐的中间体。^[1]它还用于漂白木浆和布^[27]，也是半导体工业的刻蚀剂。^[28]

参考资料

[1]
Wojtowicz, John A., Dichlorine Monoxide, Hypochlorous Acid, and Hypochlorites, Hoboken, NJ, USA: John Wiley & Sons, Inc., 2004-04-16, doi:10.1002/0471238961.0409030823151020.a01.pub2
[2]
Cady, George H.; Naughton, James M.; Dexter, Theodore H. Chlorine(I) Compounds. Inorganic Syntheses. Hoboken, NJ, USA: John Wiley & Sons, Inc. 2007-01-05. ISSN 1934-4716. doi:10.1002/9780470132364.ch44.
[3]
CHLORINE MONOXIDE. CAMEO Chemicals. National Oceanic and Atmospheric Administration. [12 May 2015]. （原始内容存档于2015-11-17）.
[4]
Balard, A.J. Recherches sur la nature des combinaisons décolorantes du chlore [Investigations into the nature of bleaching compounds of chlorine]. Annales de Chimie et de Physique. 2nd series. 1834, 57: 225–304 [2023-02-19]. （原始内容存档于2020-02-10）（法语）.
[5]
Renard, J. J.; Bolker, H. I. The chemistry of chlorine monoxide (dichlorine monoxide). Chemical Reviews. 1 August 1976, 76 (4): 487–508. doi:10.1021/cr60302a004.
[6]
Hinshelwood, Cyril Norman; Prichard, Charles Ross. CCCXIII.—A homogeneous gas reaction. The thermal decomposition of chlorine monoxide. Part I. Journal of the Chemical Society, Transactions. 1923, 123: 2730–2738. doi:10.1039/CT9232302730.
[7]
Herberich, G. E.; Jackson, R. H.; Millen, D. J. The microwave spectrum of dichlorine oxide. Molecular structure, centrifugal distortion coefficients, and force field. Journal of the Chemical Society A: Inorganic, Physical, Theoretical (Royal Society of Chemistry (RSC)). 1966: 336. ISSN 0022-4944. doi:10.1039/j19660000336.
[8]
Minkwitz, R.; Bröchler, R.; Borrmann, H. Tieftemperatur-Kristallstruktur von Dichlormonoxid, Cl₂O. Zeitschrift für Kristallographie. 1 January 1998, 213 (4): 237–239. Bibcode:1998ZK....213..237M. doi:10.1524/zkri.1998.213.4.237.
[9]
Davis, D. S. Nomograph for the Solubility of Chlorine Monoxide in Water. Industrial & Engineering Chemistry. 1942, 34 (5): 624. doi:10.1021/ie50389a021.
[10]
Powell, Steven C. The active species in drinking water chlorination: the case for Cl₂O. Environmental Science & Technology. 1 May 2010, 44 (9): 3203. Bibcode:2010EnST...44.3203P. PMID 20302368. doi:10.1021/es100800t.
[11]
Oppermann, H. Untersuchungen an Vanadinoxidchloriden und Vanadinchloriden. I. Gleichgewichte mit VOCl3, VO2Cl und VOCl2. Zeitschrift für anorganische und allgemeine Chemie. 1967, 351 (3–4): 113–126. doi:10.1002/zaac.19673510302.
[12]
Dehnicke, Kurt. Titan(IV)-Oxidchlorid TiOCl2. Zeitschrift für anorganische und allgemeine Chemie. 1961, 309 (5–6): 266–275. doi:10.1002/zaac.19613090505.
[13]
Dehnicke, Kurt. Über die Oxidchloride PO2Cl, AsO2Cl und SbO2Cl. Chemische Berichte. 1 December 1964, 97 (12): 3358–3362. doi:10.1002/cber.19640971215.
[14]
Martin, H. Kinetic Relationships between Reactions in the Gas Phase and in Solution. Angewandte Chemie International Edition in English. 1 January 1966, 5 (1): 78–84. doi:10.1002/anie.196600781.
[15]
Schmeisser, Martin; Ruff, John K.; Lustig, Max. Chlorine(I) Nitrate. Inorganic Syntheses. Hoboken, NJ, USA: John Wiley & Sons, Inc. 2007-01-05. ISSN 1934-4716. doi:10.1002/9780470132401.ch34.
[16]
Schack, Carl J.; Lindahl, C. B.; Pilipovich, Donald; Christe, Karl O. Chlorine trifluoride oxide. IV. Reaction chemistry. Inorganic Chemistry (American Chemical Society (ACS)). 1972, 11 (9): 2201–2205. ISSN 0020-1669. doi:10.1021/ic50115a043.
[17]
Marsh, F. D.; Farnham, W. B.; Sam, D. J.; Smart, B. E. Dichlorine monoxide: a powerful and selective chlorinating reagent. Journal of the American Chemical Society. 1 August 1982, 104 (17): 4680–4682. doi:10.1021/ja00381a032.
[18]
Sivey, John D.; Roberts, A. Lynn. Assessing the Reactivity of Free Chlorine Constituents Cl₂, Cl₂O, and HOCl Toward Aromatic Ethers. Environmental Science & Technology. 21 February 2012, 46 (4): 2141–2147. Bibcode:2012EnST...46.2141S. PMID 22211432. doi:10.1021/es203094z.
[19]
Mintz, M. J.; C. Walling. t-Butyl hypochlorite. Organic Syntheses. 1969, 49: 9 [2023-02-19]. （原始内容存档于2023-02-13）.
[20]
Swain, C. Gardner; Crist, DeLanson R. Mechanisms of chlorination by hypochlorous acid. The last of chlorinium ion, Cl+. Journal of the American Chemical Society. 1 May 1972, 94 (9): 3195–3200. doi:10.1021/ja00764a050.
[21]
Sivey, John D.; McCullough, Corey E.; Roberts, A. Lynn. Chlorine Monoxide (Cl₂O) and Molecular Chlorine (Cl₂) as Active Chlorinating Agents in Reaction of Dimethenamid with Aqueous Free Chlorine. Environmental Science & Technology. 1 May 2010, 44 (9): 3357–3362. Bibcode:2010EnST...44.3357S. PMID 20302364. doi:10.1021/es9038903.
[22]
Basco, N.; Dogra, S. K. Reactions of Halogen Oxides Studied by Flash Photolysis. II. The Flash Photolysis of Chlorine Monoxide and of the ClO Free Radical. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences. 22 June 1971, 323 (1554): 401–415. Bibcode:1971RSPSA.323..401B. S2CID 98084403. doi:10.1098/rspa.1971.0112.
[23]
Cady, George H.; Brown, Robert E. Minimum Explosive Concentration of Chlorine Monoxide Diluted with Oxygen. Journal of the American Chemical Society. September 1945, 67 (9): 1614–1615. doi:10.1021/ja01225a501.
[24]
Iredale, T.; Edwards, T. G. Photoreaction of Chlorine Monoxide and Hydrogen. Journal of the American Chemical Society. April 1937, 59 (4): 761. doi:10.1021/ja01283a504.
[25]
Wallace, Janet I.; Goodeve, C. F. The heats of dissociation of chlorine monoxide and chlorine dioxide. Transactions of the Faraday Society. 1 January 1931, 27: 648. doi:10.1039/TF9312700648.
[26]
Pilipovich, Donald; Lindahl, C. B.; Schack, Carl J.; Wilson, R. D.; Christe, Karl O. Chlorine trifluoride oxide. I. Preparation and properties. Inorganic Chemistry. 1972, 11 (9): 2189–2192. ISSN 0020-1669. doi:10.1021/ic50115a040.
[27]
US 3619349A,Norman Liebergott, Henry Irving Bolker,“Bleaching of shredded or fluffed cellulosic pulp with gaseous chlorine monoxide”,发表于1971-11-09
[28]
US 5200032A,Keiji Shinohara,“Dry etching method”,发表于1993-04-06

延伸阅读

钟兴厚，萧文锦，袁启华，娄润和。《无机化学丛书》第六卷，卤素、铜分族、锌分族。北京：科学出版社，1984年。

[:0-1] [1]
Wojtowicz, John A., Dichlorine Monoxide, Hypochlorous Acid, and Hypochlorites, Hoboken, NJ, USA: John Wiley & Sons, Inc., 2004-04-16, doi:10.1002/0471238961.0409030823151020.a01.pub2

[2] [2]
Cady, George H.; Naughton, James M.; Dexter, Theodore H. Chlorine(I) Compounds. Inorganic Syntheses. Hoboken, NJ, USA: John Wiley & Sons, Inc. 2007-01-05. ISSN 1934-4716. doi:10.1002/9780470132364.ch44.

[3] [3]
CHLORINE MONOXIDE. CAMEO Chemicals. National Oceanic and Atmospheric Administration. [12 May 2015]. （原始内容存档于2015-11-17）.

[4] [4]
Balard, A.J. Recherches sur la nature des combinaisons décolorantes du chlore [Investigations into the nature of bleaching compounds of chlorine]. Annales de Chimie et de Physique. 2nd series. 1834, 57: 225–304 [2023-02-19]. （原始内容存档于2020-02-10）（法语）.

[review-5] [5]
Renard, J. J.; Bolker, H. I. The chemistry of chlorine monoxide (dichlorine monoxide). Chemical Reviews. 1 August 1976, 76 (4): 487–508. doi:10.1021/cr60302a004.

[6] [6]
Hinshelwood, Cyril Norman; Prichard, Charles Ross. CCCXIII.—A homogeneous gas reaction. The thermal decomposition of chlorine monoxide. Part I. Journal of the Chemical Society, Transactions. 1923, 123: 2730–2738. doi:10.1039/CT9232302730.

[7] [7]
Herberich, G. E.; Jackson, R. H.; Millen, D. J. The microwave spectrum of dichlorine oxide. Molecular structure, centrifugal distortion coefficients, and force field. Journal of the Chemical Society A: Inorganic, Physical, Theoretical (Royal Society of Chemistry (RSC)). 1966: 336. ISSN 0022-4944. doi:10.1039/j19660000336.

[8] [8]
Minkwitz, R.; Bröchler, R.; Borrmann, H. Tieftemperatur-Kristallstruktur von Dichlormonoxid, Cl₂O. Zeitschrift für Kristallographie. 1 January 1998, 213 (4): 237–239. Bibcode:1998ZK....213..237M. doi:10.1524/zkri.1998.213.4.237.

[9] [9]
Davis, D. S. Nomograph for the Solubility of Chlorine Monoxide in Water. Industrial & Engineering Chemistry. 1942, 34 (5): 624. doi:10.1021/ie50389a021.

[10] [10]
Powell, Steven C. The active species in drinking water chlorination: the case for Cl₂O. Environmental Science & Technology. 1 May 2010, 44 (9): 3203. Bibcode:2010EnST...44.3203P. PMID 20302368. doi:10.1021/es100800t.

[11] [11]
Oppermann, H. Untersuchungen an Vanadinoxidchloriden und Vanadinchloriden. I. Gleichgewichte mit VOCl3, VO2Cl und VOCl2. Zeitschrift für anorganische und allgemeine Chemie. 1967, 351 (3–4): 113–126. doi:10.1002/zaac.19673510302.

[12] [12]
Dehnicke, Kurt. Titan(IV)-Oxidchlorid TiOCl2. Zeitschrift für anorganische und allgemeine Chemie. 1961, 309 (5–6): 266–275. doi:10.1002/zaac.19613090505.

[13] [13]
Dehnicke, Kurt. Über die Oxidchloride PO2Cl, AsO2Cl und SbO2Cl. Chemische Berichte. 1 December 1964, 97 (12): 3358–3362. doi:10.1002/cber.19640971215.

[14] [14]
Martin, H. Kinetic Relationships between Reactions in the Gas Phase and in Solution. Angewandte Chemie International Edition in English. 1 January 1966, 5 (1): 78–84. doi:10.1002/anie.196600781.

[15] [15]
Schmeisser, Martin; Ruff, John K.; Lustig, Max. Chlorine(I) Nitrate. Inorganic Syntheses. Hoboken, NJ, USA: John Wiley & Sons, Inc. 2007-01-05. ISSN 1934-4716. doi:10.1002/9780470132401.ch34.

[16] [16]
Schack, Carl J.; Lindahl, C. B.; Pilipovich, Donald; Christe, Karl O. Chlorine trifluoride oxide. IV. Reaction chemistry. Inorganic Chemistry (American Chemical Society (ACS)). 1972, 11 (9): 2201–2205. ISSN 0020-1669. doi:10.1021/ic50115a043.

[17] [17]
Marsh, F. D.; Farnham, W. B.; Sam, D. J.; Smart, B. E. Dichlorine monoxide: a powerful and selective chlorinating reagent. Journal of the American Chemical Society. 1 August 1982, 104 (17): 4680–4682. doi:10.1021/ja00381a032.

[18] [18]
Sivey, John D.; Roberts, A. Lynn. Assessing the Reactivity of Free Chlorine Constituents Cl₂, Cl₂O, and HOCl Toward Aromatic Ethers. Environmental Science & Technology. 21 February 2012, 46 (4): 2141–2147. Bibcode:2012EnST...46.2141S. PMID 22211432. doi:10.1021/es203094z.

[19] [19]
Mintz, M. J.; C. Walling. t-Butyl hypochlorite. Organic Syntheses. 1969, 49: 9 [2023-02-19]. （原始内容存档于2023-02-13）.

[Swain-20] [20]
Swain, C. Gardner; Crist, DeLanson R. Mechanisms of chlorination by hypochlorous acid. The last of chlorinium ion, Cl+. Journal of the American Chemical Society. 1 May 1972, 94 (9): 3195–3200. doi:10.1021/ja00764a050.

[Sivey-21] [21]
Sivey, John D.; McCullough, Corey E.; Roberts, A. Lynn. Chlorine Monoxide (Cl₂O) and Molecular Chlorine (Cl₂) as Active Chlorinating Agents in Reaction of Dimethenamid with Aqueous Free Chlorine. Environmental Science & Technology. 1 May 2010, 44 (9): 3357–3362. Bibcode:2010EnST...44.3357S. PMID 20302364. doi:10.1021/es9038903.

[22] [22]
Basco, N.; Dogra, S. K. Reactions of Halogen Oxides Studied by Flash Photolysis. II. The Flash Photolysis of Chlorine Monoxide and of the ClO Free Radical. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences. 22 June 1971, 323 (1554): 401–415. Bibcode:1971RSPSA.323..401B. S2CID 98084403. doi:10.1098/rspa.1971.0112.

[23] [23]
Cady, George H.; Brown, Robert E. Minimum Explosive Concentration of Chlorine Monoxide Diluted with Oxygen. Journal of the American Chemical Society. September 1945, 67 (9): 1614–1615. doi:10.1021/ja01225a501.

[24] [24]
Iredale, T.; Edwards, T. G. Photoreaction of Chlorine Monoxide and Hydrogen. Journal of the American Chemical Society. April 1937, 59 (4): 761. doi:10.1021/ja01283a504.

[25] [25]
Wallace, Janet I.; Goodeve, C. F. The heats of dissociation of chlorine monoxide and chlorine dioxide. Transactions of the Faraday Society. 1 January 1931, 27: 648. doi:10.1039/TF9312700648.

[PilipovichLindahl1972-26] [26]
Pilipovich, Donald; Lindahl, C. B.; Schack, Carl J.; Wilson, R. D.; Christe, Karl O. Chlorine trifluoride oxide. I. Preparation and properties. Inorganic Chemistry. 1972, 11 (9): 2189–2192. ISSN 0020-1669. doi:10.1021/ic50115a040.

[27] [27]
US 3619349A,Norman Liebergott, Henry Irving Bolker,“Bleaching of shredded or fluffed cellulosic pulp with gaseous chlorine monoxide”,发表于1971-11-09

[28] [28]
US 5200032A,Keiji Shinohara,“Dry etching method”,发表于1993-04-06

[4]

[1]

[2]

[3]

[5]

[6]

[7]

[8]

[9]

[10]

[11]

[12]

[13]

[14]

[15]

[16]

[17]

[18]

[19]

[20]

[21]

[22]

[23]

[24]

[25]

[26]

[27]

[28]