Periodic acid


Periodic acid is the highest oxoacid of iodine, in which the iodine exists in oxidation state +7. Like all periodates it can exist in two forms: orthoperiodic acid, with the chemical formula H5IO6 and metaperiodic acid, which has the formula HIO4.
Periodic acid was discovered by Heinrich Gustav Magnus and C. F. Ammermüller in 1833.

Synthesis

Modern industrial scale production involves the oxidation of a solution of sodium iodate under alkaline conditions, either electrochemically on a PbO2 anode, or by treatment with chlorine:
Orthoperiodic acid can be dehydrated to give metaperiodic acid by heating to 100 °C under reduced pressure.
Further heating to around 150 °C gives iodine pentoxide rather than the expected anhydride diiodine heptoxide. Metaperiodic acid can also be prepared from various orthoperiodates by treatment with dilute nitric acid.

Properties

Orthoperiodic acid has a number of acid dissociation constants. The pKa of metaperiodic acid has not been determined.
There being two forms of periodic acid, it follows that two types of periodate salts are formed. For example, sodium metaperiodate, NaIO4, can be synthesised from HIO4 while sodium orthoperiodate, Na5IO6 can be synthesised from H5IO6.

Structure

Orthoperiodic acid forms monoclinic crystals consisting of a slightly deformed IO6 octahedron interlinked via bridging hydrogens. Five I-O bond distances are in the range 1.87-1.91 Å and one I-O bond is 1.78 Å.
The structure of metaperiodic acid also includes IO6 octahedra, however these are connected via cis-edge-sharing with bridging oxygens to form one-dimensional infinite chains.

Reactions

Like all periodates periodic acid can be used to cleave various 1,2-difunctional compounds. Most notably periodic acid will cleave vicinal diols into two aldehyde or ketone fragments.
This can be useful in determining the structure of carbohydrates as periodic acid can be used to open saccharide rings. 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 instead of DNA as deoxyribose does not have vicinal diols.
Periodic acid is also used in as an oxidising agent of moderate strength.

Other oxyacids

Periodate is part of a series of oxyacids in which iodine can assume oxidation states of −1, +1, +3, +5, or +7. A number of neutral iodine oxides are also known.
Iodine oxidation state−1+1+3+5+7
NameHydrogen iodideHypoiodous acidIodous acidIodic acidPeriodic acid
FormulaHIHIOHIO2HIO3HIO4 or H5IO6