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{{chembox |
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{{chembox |
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| verifiedrevid = 443636562 |
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| verifiedrevid = 449829633 |
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| ImageFile = Dichlorine-heptoxide-3D-balls.png |
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| ImageFile = Dichlorine heptoxide.svg |
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| ImageSize = |
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| ImageSize = 180 |
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| ImageFile1 = Dichlorine-heptoxide-3D-balls.png |
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| ImageSize1 = 180 |
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| IUPACName = Dichlorine heptoxide |
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| IUPACName = Dichlorine heptoxide |
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| OtherNames = Chlorine(VII) oxide; Perchloric anhydride; (Perchloryloxy)chlorane trioxide |
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| OtherNames = Chlorine(VII) oxide; Perchloric anhydride; (Perchloryloxy)chlorane trioxide |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 109884 |
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| ChemSpiderID = 109884 |
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| InChI = 1/Cl2O7/c3-1(4,5)9-2(6,7)8 |
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| InChI = 1.001/Cl2O7/c3-1(4,5)9-2(6,7)8 |
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| InChIKey = SCDFUIZLRPEIIH-UHFFFAOYAG |
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| InChIKey = SCDFUIZLRPEIIH-UHFFFAOYAG |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = SCDFUIZLRPEIIH-UHFFFAOYSA-N |
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| StdInChIKey = SCDFUIZLRPEIIH-UHFFFAOYSA-N |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 10294-48-1 |
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| PubChem = 123272 |
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| CASNo = 12015-53-1 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = 22MM1X86NB |
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| PubChem = 123272 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 52356 |
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| ChEBI = 52356 |
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| SMILES = O=Cl(=O)(=O)OCl(=O)(=O)=O |
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| SMILES = O=Cl(=O)(=O)OCl(=O)(=O)=O |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| Formula = Cl<sub>2</sub>O<sub>7</sub> |
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| Formula = Cl<sub>2</sub>O<sub>7</sub> |
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| MolarMass = 182.901 g/mol |
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| MolarMass = 182.901 g/mol |
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| Appearance = colorless oil |
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| Appearance = colorless liquid, colorless gas |
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| Density = 1900 kg m<sup>-3</sup> |
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| Density = 1.9 g/cm<sup>3</sup> |
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| MeltingPt = −91.5 °C |
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| MeltingPtC = −91.57 |
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| BoilingPt = 82 °C |
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| BoilingPtC = 82.07 |
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| Solubility = |
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| Solubility = hydrolyzes to form ] |
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| Section3 = {{Chembox Hazards |
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| Section3={{Chembox Thermochemistry |
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| DeltaHf = 275.7{{nbsp}}kJ/mol |
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| MainHazards = oxidizer, contact explosive<ref name="Holl">{{cite book|title = Inorganic chemistry | first1 = Arnold F. | last1 = Holleman | first2 = Egon | last2 = Wiberg | others = Translated by Mary Eagleson, William Brewer | publisher = Academic Press | year = 2001 | isbn = 0123526515 | page = 464 | location = San Diego}}</ref> |
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| FlashPt = |
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| Autoignition = |
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|Section4={{Chembox Hazards |
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| NFPA-H = 3 |
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| NFPA-F = 0 |
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| NFPA-R = 3 |
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| NFPA-S = OX |
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| MainHazards = oxidizer, contact explosive<ref name="Holl">{{cite book|title = Inorganic chemistry | first1 = Arnold F. | last1 = Holleman | first2 = Egon | last2 = Wiberg | translator = Mary Eagleson | translator2 = William Brewer | publisher = Academic Press | year = 2001 | isbn = 0-12-352651-5 | page = 464 | location = San Diego}}</ref> |
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| FlashPt = |
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| AutoignitionPt = |
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|Section5={{Chembox Related |
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| OtherCompounds = ] |
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'''Dichlorine heptoxide''' is the ] with the ] Cl<sub>2</sub>O<sub>7</sub>. This ] is the ] of ]. It is produced by the careful distillation of perchloric acid in the presence of the dehydrating agent ]:<ref name="Holl" /> |
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'''Dichlorine heptoxide''' is the ] with the ] Cl<sub>2</sub>O<sub>7</sub>. This ] is the ] of ]. It is produced by the careful distillation of perchloric acid in the presence of the dehydrating agent ]:<ref name="Holl" /> |
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:2 HClO<sub>4</sub> + P<sub>4</sub>O<sub>10</sub> → Cl<sub>2</sub>O<sub>7</sub> + H<sub>2</sub>P<sub>4</sub>O<sub>11</sub> |
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:2 HClO<sub>4</sub> + P<sub>4</sub>O<sub>10</sub> → Cl<sub>2</sub>O<sub>7</sub> + H<sub>2</sub>P<sub>4</sub>O<sub>11</sub> |
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The chorine(VII) oxide can be distilled off from the mixture. |
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The chlorine(VII) oxide can be distilled off from the mixture. |
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It may also be formed by illumination on mixtures of chlorine and ].<ref>{{cite doi|10.1021/ja01320a506}}</ref> It slowly ] back to ], which is also hazardous when ]. |
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It may also be formed by illumination of mixtures of chlorine and ] with blue light.<ref>{{Cite journal| first1 = A. C.| title = The Formation of Chlorine Heptoxide on Illumination of Mixtures of Chlorine and Ozone| first2 = G. K.| last1 = Byrns| journal = Journal of the American Chemical Society| volume = 56| issue = 5| pages = 1250–1251| year = 1934| doi = 10.1021/ja01320a506| last2 = Rollefson}}</ref> It slowly ] back to ]. |
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==Structure== |
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==Structure== |
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Cl<sub>2</sub>O<sub>7</sub> is an ] molecule, meaning it is intrinsically unstable, decomposing to its constituent elements with release of energy:<ref>{{Cite journal|last=Martin|first=Jan M. L|date=2006-10-12|title=Heats of formation of perchloric acid, HClO<sub>4</sub>, and perchloric anhydride, Cl<sub>2</sub>O<sub>7</sub>. Probing the limits of W1 and W2 theory|journal=Journal of Molecular Structure: THEOCHEM|series=Modelling Structure and Reactivity: the 7th triennial conference of the World Association of Theoritical and Computational Chemists (WATOC 2005)|volume=771|issue=1|pages=19–26|doi=10.1016/j.theochem.2006.03.035|issn=0166-1280|arxiv=physics/0508076|s2cid=98385268 }}</ref> |
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Cl<sub>2</sub>O<sub>7</sub> is an endothermic molecule, which means that it is intrinsically unstable. |
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:2 Cl<sub>2</sub>O<sub>7</sub> → 2 Cl<sub>2</sub> + 7 O<sub>2</sub> (ΔH = 135 kJ/mol) |
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:2 Cl<sub>2</sub>O<sub>7</sub> → 2 Cl<sub>2</sub> + 7 O<sub>2</sub> (Δ''H°'' = –132 kcal/mol) |
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Cl<sub>2</sub>O<sub>7</sub> is bent with Cl-O-Cl angle of 118.6° giving the molecule C<sub>2</sub> ]. The terminal Cl-O distances are 1.709 Å and the Cl=O distances are 1.405 Å.<ref name=Holl/> In this compound, chlorine exists in its highest formal ] of +7, although the bonding in this molecule is significantly covalent. |
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Dichlorine heptoxide is a covalent compound consisting of two ClO<sub>3</sub> portions linked by an oxygen atom. It has an overall ] (C<sub>2</sub> ]), with a Cl−O−Cl angle of 118.6°. The chlorine–oxygen ]s are 1.709 Å in the central region and 1.405 Å within each ClO<sub>3</sub> cluster.<ref name=Holl/> In this compound, chlorine exists in its highest formal ] of +7. |
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==Chemistry== |
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==Chemistry== |
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Dichlorine heptoxide reacts with primary and secondary ]s in ] solution to yield ''N''-perchloryls:<ref>{{cite doi|10.1021/ja00817a034}}</ref> |
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Dichlorine heptoxide reacts with primary and secondary ]s in ] solution to yield perchloric amides:<ref>{{Cite journal| first1 = C. D.| first2 = K.| title = Reactions of dichlorine heptoxide with amines| last1 = Beard| journal = Journal of the American Chemical Society| volume = 96| issue = 10| pages = 3237–3239| year = 1974| doi = 10.1021/ja00817a034| last2 = Baum}}</ref> |
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:2 {{chem|RNH|2}} + {{chem|Cl|2|O|7}} → 2 {{chem|RNHClO|3}} + {{chem|H|2|O}} |
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:2 {{chem|R|2|NH}} + {{chem|Cl|2|O|7}} → 2 {{chem|R|2|NClO|3}} + {{chem|H|2|O}} |
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:2 {{chem|RNH|2}} + {{chem|Cl|2|O|7}} → 2 {{chem|RNHClO|3}} + {{chem|H|2|O}} |
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It also reacts with ]s to give alkyl perchlorates. For example, it reacts with ] in carbon tetrachloride solution to yield isopropyl perchlorate and 1-chloro-2-propyl perchlorate.<ref>{{cite doi|10.1021/jo00871a048}}</ref> |
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:2 {{chem|R|2|NH}} + {{chem|Cl|2|O|7}} → 2 {{chem|R|2|NClO|3}} + {{chem|H|2|O}} |
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It also reacts with ]s to give alkyl perchlorates. For example, it reacts with ] in carbon tetrachloride solution to yield isopropyl perchlorate and 1-chloro-2-propyl perchlorate.<ref>{{Cite journal| first1 = K. .| title = Reactions of dichlorine heptoxide with olefins| journal = The Journal of Organic Chemistry| last1 = Baum| volume = 41| issue = 9| pages = 1663–1665| year = 1976| doi = 10.1021/jo00871a048}}</ref> |
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Dichlorine heptoxide reacts with ]s to form alkyl perchlorates.<ref>{{Cite journal |last1=Baum |first1=Kurt |last2=Beard |first2=Charles D. |date=1974-05-01 |title=Reactions of dichlorine heptoxide with alcohols |url=https://pubs.acs.org/doi/abs/10.1021/ja00817a033 |journal=Journal of the American Chemical Society |language=en |volume=96 |issue=10 |pages=3233–3237 |doi=10.1021/ja00817a033 |issn=0002-7863}}</ref> |
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Dichlorine heptoxide is a strongly acidic oxide, and in solution it forms an equilibrium with perchloric acid. |
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==Safety== |
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==Safety== |
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| publisher = CRC Press |
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| publisher = CRC Press |
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| year = 1998 |
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| year = 1998 |
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| isbn = 1566702232 |
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| isbn = 1-56670-223-2 |
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| page = |
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| page = 260 |
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| url-access = registration |
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| url = https://archive.org/details/lewisdictionaryo0000lewi/page/260 |
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}}</ref> Nevertheless, it is less strongly oxidising than the other chlorine oxides, and does not attack ], ], or ] when cold.<ref name="Holl" /> It has the same effects on the human body as elemental ], and requires the same precautions.<ref>{{cite encyclopedia |
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}}</ref> Nevertheless, it is less strongly oxidising than the other chlorine oxides, and does not attack ], ], or ] when cold.<ref name="Holl" /> It has the same effects on the human body as elemental ], and requires the same precautions.<ref>{{cite encyclopedia |
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| editor = Jeanne Mager Stellman |
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| editor = Jeanne Mager Stellman |
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| encyclopedia = Encyclopaedia of occupational health and safety |
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| encyclopedia = Encyclopaedia of occupational health and safety |
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| edition = 4th |
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| edition = 4th |
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| isbn = 9221098176 |
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| isbn = 92-2-109817-6 |
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| year = 1998 |
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| year = 1998 |
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| publisher = International Labour Organization |
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| publisher = International Labour Organization |
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| page = |
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| page = 104.210 |
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| url = https://archive.org/details/encyclopaediaofo0003unse/page/104 |
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