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高碘酸盐

高碘酸盐
The metaperiodate ion
The orthoperiodate ion
系统名
tetraoxoiodate(1−)
hexaoxoiodate(5−)
识别
CAS号 15056-35-6(偏高碘酸盐)  checkY
PubChem 167232(偏高碘酸盐)
6857432(原高碘酸盐)
ChemSpider 146311 (偏高碘酸盐), 5256770 (原高碘酸盐)
SMILES
 
  • [O-][I+3]([O-])([O-])[O-]
    [O-][I+]([O-])([O-])([O-])([O-])[O-]
InChI
 
  • 1S/HIO4/c2-1(3,4)5/h(H,2,3,4,5)/p-1 (偏高碘酸盐)
    1S/H5IO6/c2-1(3,4,5,6)7/h(H5,2,3,4,5,6,7)/p-5(原高碘酸盐)
InChIKey KHIWWQKSHDUIBK-UHFFFAOYSA-M(偏高碘酸盐)
TWLXDPFBEPBAQB-UHFFFAOYSA-I(原高碘酸盐)
性质
化学式 IO4 IO65-
相关物质
其他阴离子 高氯酸盐
高溴酸盐
高锰酸盐
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

高碘酸盐 /pəˈr.ədt/ 是一种阴离子 ,由组成。它是碘含氧阴离子里碘可以达到的最高氧化态,其中碘的氧化态为 +7。不像其它高卤酸根,例如高氯酸根,高碘酸根有两种形态:偏高碘酸根 IO
4
原高碘酸根 IO5−
6
。在这一点上,它与碲酸盐类似。 高碘酸根可以和阳离子结合,形成高碘酸盐,也就是高碘酸的盐。

高碘酸盐是被海因里希·马格努斯和 C. F. Ammermüller发现的。他们也在 1833年发现了高碘酸。[1]

制备

传统上,高碘酸盐最常以高碘酸氢钠(Na3H2IO6)的形式产生。 [2] 这是可商购的,但是也可以通过用氢氧化钠来氧化碘酸盐来生产。 [3]代替氯来氧化碘化物也是可行的。

NaIO3 + Cl2 + 4 NaOH → Na3H2IO6 + 2 NaCl + H2O
NaI + 4 Br2 + 10 NaOH → Na3H2IO6 + 8 NaBr + 4 H2O

现代工业规模生产涉及在PbO2阳极上碘酸盐的电化学氧化,并具有以下标准电极电位

H5IO6 + H+ + 2 eIO
3
+ 3 H2O      E° = 1.6 V[4]

偏高碘酸盐一般由硝酸来对高碘酸氢钠进行脱水而成的。[2]在 100 °C 的真空下,高碘酸氢钠也可以脱水成高碘酸盐。

Na3H2IO6 + 2 HNO3 → NaIO4 + 2 NaNO3 + 2 H2O
H5IO6 → HIO4 + 2 H2O

它们也可以由碘酸盐和强氧化剂如:次氯酸盐反应而成:

NaIO3 + NaOCl → NaIO4 + NaCl

形态和变化

高碘酸盐可以以多种形式存在于水性介质中,其中pH是控制因素。原高碘酸盐具有许多酸解离常数[5][6]

H5IO6 H
4
IO
6
+ H+     pKa = 3.29
H
4
IO
6
H
3
IO2−
6
+ H+     pKa = 8.31
H
3
IO2−
6
H
2
IO3−
6
+ H+     pKa = 11.60

原高碘酸四氢根和偏高碘酸根存在平衡。

H
4
IO
6
IO
4
+ 2 H2O,      K = 29

由于这个原因,原高碘酸盐经常被认为是偏高碘酸盐的二水合物[7] 写作 IO
4
·2H2O
。 但是,由于H5IO6X射线晶体学结果显示它有5个一样的I-OH基团,因此该描述并不准确。 [8]

在极端的pH值下,高碘酸盐可能会形成其他物质。 在碱性条件下,高碘酸三氢盐会脱水形成二碘酸盐。

H
3
IO2−
6
H
2
I
2
O4−
10
+ 2 H2O,      K = 820

在超强酸下,高碘酸也会被质子化,形成六氢氧化碘阳离子[9]

H
6
IO+
6
⇌ H5IO6 + H+,      pKa = −0.8

结构和成键

不管是偏高碘酸根还是原高碘酸根,碘原子都处于超价状态,也就是可以形成超过符合八隅体规则所需要的键的数量的键。这可以用配位键进行了解释,也证实了这些分子中不存在双键。 [10]

高碘酸根的真正结构就看阳离子是什么,但是平均而言,原高碘酸盐采用略有变形的八面体结构,X射线衍射显示I–O键长为1.89 Å[11][8] 偏高碘酸根的结构则是变形四面体, I–O 键长为 1.78 Å。[12][13]

反应

热分解

高碘酸盐在水热条件下进行热分解,可以用于制备碘酸盐[14]

2 La(H2O)3{IO4(OH)2} + 4 H5IO6 → 2 La(IO3)3·12H2O + 3 O2 + 17 H2O

裂解反应

高碘酸盐可以在各种1,2-双官能化烷烃上裂解碳-碳键。 [15][16] 最常见的例子是二醇裂解英语Glycol cleavage,它也是第一个被发现的(Malaprade反应)。 [17]二醇外,高碘酸盐还可裂解1,2-羟酮英语Hydroxy ketone1,2-二酮α-酮酸α-羟酸氨基酸[18] 1,2-胺醇[19] 1,2-二胺[20]环氧化物[21] 并形成醛,酮和羧酸。

烯烃也可以在Lemieux–Johnson氧化反应中被氧化和裂解。 这利用了四氧化锇的催化负载,该负载由高碘酸盐原位再生。 整个过程等同于臭氧化反应

裂解反应通过称为高碘酸酯的环状中间体进行。 其形成可能受pH和温度的影响 [22] 但是底物的几何形状影响最大,cis-二醇的反应明显快于trans-二醇。 [23] 反应是放热的,并且通常在0℃下进行。 由于高碘酸盐仅易溶于水,因此反应通常在水性介质中进行。 在溶解度很重要的情况下,可以使用高碘酸,因为它可溶于醇。 相转移催化剂多相液体英语Multiphasic liquid混合物中反应也有效。 在极端情况下,高碘酸盐可能会交换四乙酸铅,后者以相似的方式反应并溶于有机溶剂(Criegee反应)。

高碘酸盐裂解通常在分子生物化学中用于修饰糖类环的目的,因为许多五元和六元糖具有邻位二醇。 从历史上看,它也被用来确定单糖的结构。 [24][25]

高碘酸盐的裂解可以以工业规模进行,以形成在造纸中使用的二醛淀粉英语Dialdehyde starch[26]

氧化反应

高碘酸盐都是强氧化剂。 它们可以氧化邻苯二酚1,2-苯醌,把对苯二酚氧化成1,4-苯醌[27] 硫化物也会被它们氧化成亚砜[28] 高碘酸盐的氧化性很强,可以制备其它强氧化剂如:高锰酸盐[29] 四氧化锇[30]四氧化钌

利基用途

高碘酸盐对于某些基氧化物是有高度选择性的蚀刻剂。 [31]

显微镜学中使用的几种染色剂基于高碘酸盐(例如PAS染色法琼斯氏染色英语Jones' stain

高碘酸盐也已经用作烟火制造术中的氧化剂。 [32] 2013年,美国陆军宣布将用高碘酸钠替代对环境有害的化学物硝酸钡高氯酸钾,用于示踪弹药。 [33]

其它含氧阴离子

高碘酸盐是的含氧阴离子之一。碘可以形成氧化态为 −1(其实不是), +1, +3, +5或 +7 的含氧阴离子。 一系列中性的碘的氧化物也是已知的。

碘的氧化态 −1 +1 +3 +5 +7
名字 碘化物 次碘酸盐 亚碘酸盐 碘酸盐 高碘酸盐
化学式 I IO IO
2
IO
3
IO
4
IO5−
6
结构 The iodide ion The iodate ion The orthoperiodate ionThe metaperiodate ion

参见

参考资料

  1. ^ Ammermüller, F.; Magnus, G. Ueber eine neue Verbindung des Jods mit Sauerstoff, die Ueberjodsäure. Annalen der Physik und Chemie. 1833, 104 (7): 514–525. Bibcode:1833AnP...104..514A. doi:10.1002/andp.18331040709 (德语). 
  2. ^ 2.0 2.1 Riley, edited by Georg Brauer; translated by Scripta Technica, Inc. Translation editor Reed F. Handbook of preparative inorganic chemistry. Volume 1 2nd. New York, N.Y.: Academic Press. 1963: 323–324. ISBN 012126601X. 
  3. ^ Hill, Arthur E. Ternary Systems. VII. The Periodates of the Alkali Metals. Journal of the American Chemical Society. October 1928, 50 (10): 2678–2692. doi:10.1021/ja01397a013. 
  4. ^ Parsons, Roger. Handbook of electrochemical constants. Butterworths Scientific Publications Ltd. 1959: 71. 
  5. ^ Aylett, founded by A.F. Holleman; continued by Egon Wiberg; translated by Mary Eagleson, William Brewer; revised by Bernhard J. Inorganic chemistry 1st English ed., [edited] by Nils Wiberg. San Diego, Calif.: Berlin: Academic Press, W. de Gruyter. 2001: 454. ISBN 0123526515. 
  6. ^ Burgot, Jean-Louis. Ionic equilibria in analytical chemistry. New York: Springer. : 358. ISBN 1441983821. 
  7. ^ Ropp, Richard C. Encyclopedia of the alkaline earth compounds. Oxford: Elsevier Science. : 96. ISBN 0444595538. 
  8. ^ 8.0 8.1 Feikema, Y. D. The crystal structures of two oxy-acids of iodine. I. A study of orthoperiodic acid, H5IO6, by neutron diffraction. Acta Crystallographica. 1966, 20 (6): 765–769. doi:10.1107/S0365110X66001828. 
  9. ^ Greenwood, N.N.; Earnshaw, A. Chemistry of the elements有限度免费查阅,超限则需付费订阅 2nd. Oxford: Butterworth-Heinemann. 2006: 874. ISBN 0750633654. 
  10. ^ Ivanov, A.; Popov, A.; Boldyrev, A.; Zhdankin, V. The I=X (X = O,N,C) Double Bond in Hypervalent Iodine Compounds: Is it Real?. Angew. Chem. Int. Ed. 2014, 53: 9617–9621. doi:10.1002/anie.201405142. 
  11. ^ Tichý, K.; Rüegg, A.; Beneš, J. Neutron diffraction study of diammonium trihydrogen periodate, (NH4)2H3IO6, and its deuterium analogue, (ND4)2D3IO6. Acta Crystallographica Section B. 1980, 36 (5): 1028–1032. doi:10.1107/S0567740880005225. 
  12. ^ Levason, W.; Webster, M. Ammonium tetraoxoiodate(VII). Acta Crystallographica Section C. 15 June 1999, 55 (6): IUC9900052. doi:10.1107/S0108270199099394可免费查阅. 
  13. ^ Kálmán, A.; Cruickshank, D. W. J. Refinement of the structure of NaIO4. Acta Crystallographica Section B. 1970, 26 (11): 1782–1785. doi:10.1107/S0567740870004880. 
  14. ^ Hydrothermal Synthesis of Rare Earth Iodates from the Corresponding Periodates: Structures of Sc(IO3)3, Y(IO3)3 · 2 H2O, La(IO3)3 · 1/2 H2O and Lu(IO3)3 · 2 H2O. doi:10.1002/1521-3749(200201)628:1<198::AID-ZAAC198>3.0.CO;2-L. ZAAC. 2002.
  15. ^ Sklarz, B. Organic chemistry of periodates. Quarterly Reviews, Chemical Society. 1967, 21 (1): 3. doi:10.1039/QR9672100003. 
  16. ^ Bamford, edited by C.H.; Tipper, C.F.H. Reactions of non-metallic inorganic compounds. Amsterdam: Elsevier Pub. Co. 1972: 435. ISBN 9780080868011. 
  17. ^ L. Malaprade, Bull. Soc. Chim. Fr. 3, 1, 833 (1934)
  18. ^ Clamp, J.R.; Hough, L. The Periodate Oxidation of Amino Acids with Reference to Studies on Glycoproteins.. The Biochemical Journal. Jan 1965, 94: 17–24. PMC 1206400可免费查阅. PMID 14342227. doi:10.1042/bj0940017. 
  19. ^ Nicolet, Ben H.; Shinn, Leo A. THE ACTION OF PERIODIC ACID ON α-AMINO ALCOHOLS. Journal of the American Chemical Society. June 1939, 61 (6): 1615–1615. doi:10.1021/ja01875a521. 
  20. ^ Maros, László; Molnár-Perl, Ibolya; Schissel, Enikó; Szerdahelyi, Vilmos. Mechanism of the periodate oxidation of ethane-1,2-diamine, N,N′-dimethylethane-1,2-diamine, and 2-aminoethanol. Journal of the Chemical Society, Perkin Transactions 2. 1980, (1): 39. doi:10.1039/P29800000039. 
  21. ^ Telvekar, Vikas N.; Patel, Dharmeshkumar J.; Mishra, Sanket J. Oxidative Cleavage of Epoxides Using Aqueous Sodium Paraperiodate. Synthetic Communications: 311–315. doi:10.1080/00397910802372574. 
  22. ^ Buist, G. J.; Bunton, C. A.; Hipperson, W. C. P. The mechanism of oxidation of α-glycols by periodic acid. Part X. The oxidation of pinacol, and a general discussion of the stability of periodate esters and their role in the mechanism of oxidation. Journal of the Chemical Society B: Physical Organic. 1971: 2128. doi:10.1039/J29710002128. 
  23. ^ McMurry, John. Organic chemistry有限度免费查阅,超限则需付费订阅 8th ed., [international ed.] Singapore: Brooks/Cole Cengage Learning. 2012: 312. ISBN 084005453X. 
  24. ^ Jackson, Ernest L.; Hudson, C. S. Studies on the Cleavage of the Carbon Chain of Glycosides by Oxidation. A New Method for Determining Ring Structures and Alpha and Beta Configurations of Glycosides. Journal of the American Chemical Society. June 1937, 59 (6): 994–1003. doi:10.1021/ja01285a010. 
  25. ^ Robyt, John F. Essentials of carbohydrate chemistry. New York: Springer. 1998. ISBN 0387949518. 
  26. ^ Yu, Jiugao; Chang, Peter R.; Ma, Xiaofei. The preparation and properties of dialdehyde starch and thermoplastic dialdehyde starch. Carbohydrate Polymers. January 2010, 79 (2): 296–300. doi:10.1016/j.carbpol.2009.08.005. 
  27. ^ Weidman, S. W.; Kaiser, E. T. The Mechanism of the Periodate Oxidation of Aromatic Systems. III. A Kinetic Study of the Periodate Oxidation of Catechol. Journal of the American Chemical Society. December 1966, 88 (24): 5820–5827. doi:10.1021/ja00976a024. 
  28. ^ Leonard, Nelson J.; Johnson, Carl R. Periodate Oxidation of Sulfides to Sulfoxides. Scope of the Reaction. The Journal of Organic Chemistry. January 1962, 27 (1): 282–284. doi:10.1021/jo01048a504. 
  29. ^ Lemieux, R. U.; Rudloff, E. Von. Periodate–Permanganate Oxidations: I. Oxidation of Olefins. Canadian Journal of Chemistry. November 1955, 33 (11): 1701–1709. doi:10.1139/v55-208. 
  30. ^ Pappo, R.; Allen, Jr., D. S.; Lemieux, R. U.; Johnson, W. S. Notes - Osmium Tetroxide-Catalyzed Periodate Oxidation of Olefinic Bonds. The Journal of Organic Chemistry. 1956, 21 (4): 478–479. ISSN 0022-3263. doi:10.1021/jo01110a606. 
  31. ^ Dieter Weber, Róza Vöfély, Yuehua Chen, Yulia Mourzina, Ulrich Poppe: Variable resistor made by repeated steps of epitaxial deposition and lithographic structuring of oxide layers by using wet chemical etchants. Thin Solid Films (2013) DOI: 10.1016/j.tsf.2012.11.118
  32. ^ Moretti, Jared D.; Sabatini, Jesse J.; Chen, Gary. Periodate Salts as Pyrotechnic Oxidizers: Development of Barium- and Perchlorate-Free Incendiary Formulations. Angewandte Chemie International Edition. 9 July 2012, 51 (28): 6981–6983. PMID 22639415. doi:10.1002/anie.201202589. 
  33. ^ Picatinny to remove tons of toxins from lethal rounds. U.S. Army. [31 October 2013]. (原始内容存档于2016-10-09). 
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هذه مقالة غير مراجعة. ينبغي أن يزال هذا القالب بعد أن يراجعها محرر مغاير للذي أنشأها؛ إذا لزم الأمر فيجب أن توسم المقالة بقوالب الصيانة المناسبة. يمكن أيضاً تقديم طلب لمراجعة المقالة في الصفحة المخصصة لذلك. (أكتوبر 2023) المبنى الرئيسي، Geschwister-Scholl-Str. ماينز (الصورة: 2011) أكاديمية ا…

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Bridge in Pittsburgh, United States Thirtieth Street BridgeCoordinates40°27′50″N 79°58′45″W / 40.4640°N 79.9791°W / 40.4640; -79.9791Carries2 lanes of 30th StreetCrossesAllegheny RiverLocalePittsburghCharacteristicsDesignGirder bridgeTotal length105 feet (32 m)Longest span60 feet (18 m)Clearance below30 feet (9.1 m)HistoryOpened1986[1]Location The 30th Street Bridge is a girder bridge that carries vehicular traffic across the Allegheny R…

Rupert Clare GarsiaAdministrator of NauruIn office1933–1938Preceded byWilliam Augustin NewmanSucceeded byFrederick Royden Chalmers Personal detailsBorn9 October 1887Christchurch, New ZealandDied18 February 1954(1954-02-18) (aged 66)Canberra, Australia Commander Rupert Clare Garsia (9 October 1887 – 18 February 1954) was a New Zealand-born Royal Navy and Royal Australian Navy officer, and later Administrator of Nauru. Biography Garsia was born in Christchurch in 1887 to Captain Christoph…

Tassels dyed with BASF dyes 1901A colorant is any substance that changes the spectral transmittance or reflectance of a material.[1] Synthetic colorants are those created in a laboratory or industrial setting. The production and improvement of colorants was a driver of the early synthetic chemical industry, in fact many of today's largest chemical producers started as dye-works in the late 19th or early 20th centuries, including Bayer AG(1863).[2] Synthetics are extremely attract…

2019 nonfiction book by Howard Stern Howard Stern Comes Again AuthorHoward SternCountryUnited StatesLanguageEnglishPublisherSimon & SchusterPublication dateMay 14, 2019Media typeHardcovereBookPages560 (Hardcover)ISBN978-1-501-19429-0Preceded byMiss America  Howard Stern Comes Again is the third book by American radio personality Howard Stern, released on May 14, 2019, by Simon & Schuster. It is his first book in 24 years since the release of Miss America (1995).[1]…

Kisarazu Air Group/707th Naval Air GroupMitsubishi G3M1 White 12 of Kisarazu Naval Air Group, Ōmura, 1937.ActiveApril 1, 1936 – December 1, 1942CountryEmpire of JapanAllegianceAxis Powers of World War IIBranchImperial Japanese NavyTypeNaval aviation unitRoleBomberSizeVariedPart ofYokosuka Naval District1st Combined Air Group26th Air FlotillaGarrison/HQKisarazu Air FieldŌmura, JapanShanghai, ChinaKavieng, New IrelandRabaul, New BritainAircraft flownG3M Type 96 NellG2H Type 95G4M Type 1 B…

Not to be confused with New Zealand cricket team in Pakistan in 2022–23 (April 2023). International cricket tour New Zealand cricket team in Pakistan in 2022–23    Pakistan New ZealandDates 26 December 2022 – 13 January 2023Captains Babar Azam Tim Southee (Tests)Kane Williamson (ODIs)Test seriesResult 2-match series drawn 0–0Most runs Sarfaraz Ahmed (335) Tom Latham (281)Most wickets Abrar Ahmed (11) Ish Sodhi (13)Player of the series Sarfaraz Ahmed (Pak)One Day Internatio…

Not to be confused with the Lou Donaldson album Good Gracious!. 2010 studio album by M-PhazesGood GraciousStudio album by M-PhazesReleasedFebruary 2010 (2010-02)GenreHip hopLength66:16LabelObeseProducerM-PhazesM-Phazes chronology Good Gracious(2010) Phazed Out(2012) Good Gracious is the first album by Australian hip hop producer M-Phazes. Released in February 2010 on Obese Records, each track features different artists, including Drapht, Bliss n Eso, Illy and Forthwrite (360 an…

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