Sodium bismuthate: Difference between revisions

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| ImageFile1 = NaBiO3.jpg

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| ImageCaption1 = NaBiO₃ powder.

| ImageFile2 =

| ImageSize2 =

| ImageCaption2 = Solid state structure

| IUPACName =

| SystematicName =

| OtherNames = Sodium bismuth oxide

|Section1={{Chembox Identifiers

| CASNo = 12232-99-4

| CASNo_Ref = {{cascite|correct|CAS}}

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| UNII_Ref = {{fdacite|correct|FDA}}

| UNII = 2PR2L7N425

| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

| ChemSpiderID = 74877

| EC_number = 235-455-6

| InChI = 1S/Bi.Na.3O/q;+1;;;-1

| PubChem = 4063671

| RTECS =

| SMILES = [O-][Bi](=O)=O.[Na+]

|Section2={{Chembox Properties

| Appearance = Yellow to yellowish-brown odorless powder<ref name="ma"/>

| BoilingPt =

| Density = 6.50 g/cm³

| Formula = NaBiO₃

| MolarMass = 279.968 g/mol

| MeltingPt =

| pKa =

| pKb =

| Solubility = Insoluble in cold, decomposes in hot water<ref name="me"/>

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|Section3={{Chembox Structure

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|Section7={{Chembox Hazards

| AutoignitionPt =

| ExternalSDS =

| FlashPt =

| LD50 = 420 mg/kg (rat, oral)<ref name="ma">{{cite web|title=Sodium bismuthate|url=http://hazard.com/msds/mf/baker/baker/files/s3026.htm|publisher=Mallinckrodt Baker|date=2007-06-19}}</ref>

| MainHazards =

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| GHSPictograms = {{GHS07}}

| GHSSignalWord = Warning

| HPhrases = {{H-phrases|302|315|319|335}}

| PPhrases = {{P-phrases|261|264|270|271|280|301+312|302+352|304+340|305+351+338|312|321|330|332+313|337+313|362|403+233|405|501}}

|Section8={{Chembox Related

| OtherFunction_label =

| OtherAnions = [[Sodium antimonate]]

| OtherCations = [[Potassium bismuthate]]

| OtherCompounds = [[Sodium hexafluorobismuthate(V)]]

}}

'''Sodium bismuthate''' is an [[inorganic compound]], and a strong [[oxidiser]] with chemical formula NaBiO₃.<ref name="Green">{{Greenwood&Earnshaw2nd}}</ref> It is somewhat [[hygroscopic]],<ref name="me">{{cite book|title=The Merck index|date=2000|publisher=Chapman & Hall Electronic Pub. Division|isbn=9781584881292|edition=12th|pages=1357}}</ref> but not soluble in cold [[water]], which can be convenient since the reagent can be easily removed after the reaction. It is one of the few water insoluble sodium salts. Commercial samples may be a mixture of bismuth(V) oxide, [[sodium carbonate]] and [[sodium peroxide]].<ref>Suzuki, pp. 1-20</ref>

A related compound with the approximate formula Na₃BiO₄ also exists.<ref>{{cite thesis|last=Sascha|first=Vensky|year=2004|title=Konformationsaufklärung anorganischer Oxoanionen des Kohlenstoffs und Festkörpersynthesen durch Elektrokristallisation von Ag₃O4 und Na₃BiO₄|publisher=[[Max-Planck-Institut für Festkörperforschung, Stuttgart]]|type=Ph.D.|url=https://elib.uni-stuttgart.de/bitstream/11682/6557/1/Dissertation-S_Vensky.pdf|language=de|doi=10.18419/opus-6540}}</ref>

==Structure==

Sodium bismuthate adopts an [[ilmenite]] structure, consisting of [[octahedral molecular geometry|octahedral]] bismuth(V) centers and sodium cations. The average Bi–O distance is 2.116&nbsp;Å. The ilmenite structure is related to the corundum structure ([[aluminium oxide|Al₂O₃]]) with a layer structure formed by close packed oxygen atoms with the two different cations alternating in octahedral sites.<ref>{{cite journal|title=Neutron powder diffraction refinement of ilmenite-type bismuth oxides: ABiO₃ (A = Na, Ag)|last1=Kumada|first1=N.|last2=Kinomura|first2=N.|last3=Sleight|first3=A. W.|doi=10.1016/S0025-5408(00)00453-0|year=2000|volume=35|issue=14–15|pages=2397–2402|journal=[[Materials Research Bulletin]]}}{{Subscription or libraries|sentence|via=[[ScienceDirect]]}}</ref>

==Synthesis==

Bismuth oxidizes to the +V [[oxidation state]] only with difficulty in the absence of alkali. Synthesis is performed by making a suspension of bismuth trioxide in a boiling sodium hydroxide solution. It is then oxidized by addition of bromine to form sodium bismuthate.<ref>{{cite book | author=hrsg. von Georg Brauer. Unter Mitarb. von M. Baudler | title=Handbuch der präparativen anorganischen Chemie / 1. | publisher=Enke | publication-place=Stuttgart | date=1975 | isbn=3-432-02328-6 | oclc=310719485 | language=de |page=604}}</ref>

:Bi₂O₃ + 6 NaOH + 2 Br₂ → 2 NaBiO₃ + 4 NaBr + 3 H₂O

Another synthesis of NaBiO₃ involves oxidizing a mixture of [[sodium oxide]] and [[bismuth(III) oxide]] with air (as the source of O₂):<ref>{{cite book|title=Chemistry of the elements|vauthors=Greenwood NN|publisher=Butterworth-Heinemann|year=1997|isbn=9780080379418|edition=2nd|pages=578|display-editors=etal}}</ref>

:Na₂O + Bi₂O₃ + O₂ → 2 NaBiO₃

The procedure is analogous to the oxidation of [[manganese dioxide]] in alkali to give [[sodium manganate]].

[[File:NaBiO3.png|thumb|30px|left|Vial of NaBiO₃]]

==Reactions==

Storage conditions with moisture and high temperatures are detrimental to sodium bismuthate, as it oxidizes water, decomposing into [[sodium hydroxide]] and bismuth(III) oxide:<ref name="me"/>

:2 NaBiO₃ + H₂O → 2 NaOH + Bi₂O₃ + O₂

It is decomposed faster by [[acid]]s. In [[HCl]], NaBiO₃ also reacts to form [[chlorine gas]].<ref name="me"/>

NaBiO₃ may be used to detect manganese qualitatively and quantitatively. As a strong oxidizer, it converts almost any manganese compound to [[permanganate]], which is easily assayed [[spectrophotometrical]]ly.<ref name=Green/> To do this, some NaBiO₃ and the sample are reacted in a hot solution of sulfuric acid or nitric acid.<ref name="me"/> Permanganate has a violet color and maximum [[absorbance]] at 510&nbsp;nm. The reaction is:{{cn|date=November 2019}}

:2 Mn²⁺ + 5 NaBiO₃ + 14 H⁺ → 2 {{chem|MnO|4|−}} + 5 Bi³⁺ + 5 Na⁺ + 7 H₂O

Sodium bismuthate can perform oxidative 1,2-cleavage on [[glycol]]s, [[ketol]]s and [[alpha hydroxy acid]]s with no further oxidation of the (possible) [[aldehyde]] products:<ref name=":0">Suzuki, p. 373</ref>

:R₂C(OH)–C(OH)–'''R'''₂ → R₂C=O + O=C'''R'''₂

:R₂C(OH)–C(O)–'''R''' → R₂C=O + '''R'''COOH

:R₂C(OH)–COOH → R₂C=O + CO₂

These cleavages can be done in the presence of [[acetic]] or [[phosphoric acid]] at room temperature. Alcohols like [[methanol]] or [[ethanol]] can be used as the reaction media, as they are oxidized slowly with sodium bismuthate. [[Lead tetraacetate]] performs similar reactions, but anhydrous conditions, as required in the use of lead tetraacetate, are not necessary for sodium bismuthate.<ref name=":0"/>

NaBiO₃ can be used for lab-scale plutonium separation (see [[bismuth phosphate process]]).

==Safety==

NaBiO₃ is a mild mechanical [[Irritation|irritant]]. Upon ingestion it is moderately toxic with symptoms akin to [[lead poisoning]]: abdominal pain and vomiting. Large doses cause diarrhea and death. Continued absorption of NaBiO₃ into body causes permanent [[kidney damage]].<ref name="ma"/> These effects are due to the [[Bismuth poisoning|toxicity of bismuth]]. Oral absolute lethal dose (LD₁₀₀) of NaBiO₃ is 720&nbsp;mg/kg for rats, and 510&nbsp;mg/kg for rabbits.<ref>{{cite journal |last=Dusinska |display-authors=etal |first=M |date=2013-12-12 |title=Opinion on bismuth citrate |url=http://ec.europa.eu/health/sites/health/files/scientific_committees/consumer_safety/docs/sccs_o_147.pdf |journal=Scientific Committee on Consumer Safety |doi=10.2772/74214 |isbn=9789279301223 |id=SCCS Number: SCCS/1499/12}}</ref>

*{{cite book|last=Suzuki|first=Hitomi|title=Organobismuth Chemistry|url=https://books.google.com/books?id=qODswAbaBmsC&pg=PA8|year=2001|publisher=[[Elsevier]]|isbn=978-0-444-20528-5|editor1-first=Hitomi|editor1-last=Suzuki|editor2-first=Yoshihiro|editor2-last=Matano}}

* {{cite book|last=Brauer|first=George|date=1963|title=Handbook of Preparative Inorganic Chemistry|volume=1|pages=627–628|url=http://library.sciencemadness.org/library/books/brauer_ocr.pdf}}

===Citations===

{{Bismuth compounds}}

[[Category:Sodium compounds]]

[[Category:Bismuth compounds]]

[[Category:Oxygen compounds]]