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Sodium periodate

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Title: Sodium periodate  
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Subject: Periodic acid, Ruthenium tetroxide, Sodium nitride, Sodium zincate, Sodium permanganate
Collection: Oxidizing Agents, Periodates, Sodium Compounds
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Sodium periodate

Sodium periodate
CAS number  YesY
ChemSpider  YesY
EC number
RTECS number SD4550000
Jmol-3D images Image 1
Molecular formula NaIO4
Molar mass 213.8918 g/mol
Appearance white crystals
Density 3.865 g/cm3 (anhydrous)
3/210 g/cm3
Melting point 300 °C (572 °F; 573 K) (anhydrous)
175 °C (347 °F; 448 K) (trihydrate) (decomposes)
Solubility in water soluble
Solubility soluble in acids
Crystal structure tetragonal (anhydrous)
trigonal (trihydrate)
NFPA 704
Related compounds
Other anions sodium perchlorate, sodium perbromate
Other cations potassium periodate, periodic acid
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 N   YesY/N?)

Sodium periodate is an sodium cation and the periodate anion. It may also be regarded as the sodium salt of periodic acid. Like all periodates it can exist in two different forms: sodium metaperiodate, which has the formula NaIO4, and sodium orthoperiodate, normally this means sodium hydrogen periodate (Na2H3IO6) but the fully reacted sodium orthoperiodate salt, Na5IO6, can also be prepared. Both salts are useful oxidising agents.[1]


  • Preparation 1
  • Structure 2
  • Uses 3
  • See also 4
  • References 5


Classically, periodate was most commonly produced in the form of sodium hydrogen periodate (Na3H2IO6).[2] This is commercially available, but can also be produced by the oxidation of iodates with chlorine and sodium hydroxide.[3] Or, similarly, from iodides by oxidation with bromine and sodium hydroxide:

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

Modern industrial scale production involves the electrochemical oxidation of iodates, on a PbO2 anode, with the following standard electrode potential:

H5IO6 + H+ + 2 e → IO3 + 3 H2O   1.6 [4]

Sodium metaperiodate is can be prepared by the dehydration of sodium hydrogen periodate with nitric acid.[2]

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


Sodium metaperiodate (NaIO4) forms tetragonal crystals (space group I41/a) consisting of slightly distorted IO4 ions with average I-O bond distances of 1.775 Å; the Na+ ions are surrounded by 8 oxygen atoms at distances of 2.54 and 2.60 Å[5]

Sodium hydrogen periodate (Na2H3IO6) forms orthorhombic crystals (space group Pnnm). Iodine and sodium atoms are both surrounded by an octahedral arraigement of 6 oxygen atoms; however the NaO6 octahedron is strongly distorted. IO6 and NaO6 groups are linked via common vertices and edges.[6]

Powder diffraction indicates that Na5IO6 crystallises in the monoclinic system (space group C2/m).[7]


Sodium periodate can be used in solution to open saccharide rings between vicinal diols leaving two aldehyde groups. This process is often used in labeling saccharides with fluorescent molecules or other tags such as biotin. Because the process requires vicinal diols, periodate oxidation is often used to selectively label the 3'-termini of RNA (ribose has vicinal diols) instead of DNA as deoxyribose does not have vicinal diols.

NaIO4 is used in diols to produce two aldehydes.[8]

In 2013 US Army announced that it would replace environmentally harmful chemicals barium nitrate and potassium perchlorate with sodium metaperiodate for use in their tracer ammunition.[9]

See also


  1. ^ Andrew G. Wee, Jason Slobodian, Manuel A. Fernández-Rodríguez and Enrique Aguilar "Sodium Periodate" e-EROS Encyclopedia of Reagents for Organic Synthesis 2006. doi:10.1002/047084289X.rs095.pub2
  2. ^ a b Riley, edited by Georg Brauer ; translated by Scripta Technica, Inc. Translation editor Reed F. (1963). Handbook of preparative inorganic chemistry. Volume 1 (2nd ed. ed.). New York, N.Y.: Academic Press. pp. 323–324.  
  3. ^ Hill, Arthur E. (October 1928). "TERNARY SYSTEMS. VII. THE PERIODATES OF THE ALKALI METALS". Journal of the American Chemical Society 50 (10): 2678–2692.  
  4. ^ Parsons, Roger (1959). Handbook of electrochemical constants. Butterworths Scientific Publications Ltd. p. 71. 
  5. ^ Kálmán, A.; Cruickshank, D. W. J. (15 November 1970). "Refinement of the structure of NaIO4". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry 26 (11): 1782–1785.  
  6. ^ Jansen, Martin; Rehr, Anette (1988). "Na2H3IO6, eine Variante der Markasitstruktur". Zeitschrift für anorganische und allgemeine Chemie allgemeine Chemie (in German) 567 (1): 95–100.  
  7. ^ Betz, T.; Hoppe, R. (May 1984). "Über Perrhenate. 2. Zur Kenntnis von Li5ReO6 und Na5ReO6 – mit einer Bemerkung über Na5IO6". Zeitschrift für anorganische und allgemeine Chemie (in German) 512 (5): 19–33.  
  8. ^ McMurry, John. Organic chemistry (8th ed., [international ed.] ed.). Singapore: Brooks/Cole Cengage Learning. pp. 285–286.  
  9. ^ "Picatinny to remove tons of toxins from lethal rounds". U.S. Army. Retrieved 31 October 2013. 
  • See Fatiadi, Synthesis (1974)229-272 for a review of periodate chemistry.
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