Under electrolysis hydrogen and sodium hydroxide are formed at the cathode and chloride ions are discharged at the anode (mixed metal oxide electrode is often used).

The formation of H+ ions should make the boundary layer at the anode strongly acidic and this is observed at low chloride concentrations.

The hypochlorous acid dissociates in the bulk electrolyte where the pH is high and the hypochlorite ion diffuses back to the anode.

The remainder is discharged at the anode to form chlorate and oxygen: The autoxidation of hypochlorous acid in the bulk electrolyte proceeds according to the simplified overall equation: It is preceded by the dissociation of a part of the hypochlorous acid involved: The reaction requires a certain distance from the anode to occur to a significant degree, where the electrolyte is sufficiently buffered by the hydroxyl formed at the cathode.

Sodium chlorate may be used to control a variety of plants including morning glory, canada thistle, johnson grass, bamboo, ragwort, and St John's wort.

The herbicide is mainly used on non-crop land for spot treatment and for total vegetation control on areas including roadsides, fenceways, and ditches.

The sale of sodium chlorate as a weedkiller was banned in the European Union in 2009 citing health dangers, with existing stocks to be used within the following year.

Similarly, the Solidox welding system used pellets of sodium chlorate mixed with combustible fibers to generate oxygen.

Sodium chlorate can be mixed with sucrose sugar to make a highly energetic fuel, similar to that of gunpowder, that burns in airtight spaces.

In this case its function is to oxidize the HCl to obtain either HOCl or Cl2 (depending upon the pH) in-situ which are the active chlorinating agents.

Mixtures of chlorates and organic compounds pose a severe risk of explosions[16] Marketed formulations contain a fire retardant.

Some trade names for products containing sodium chlorate include Atlacide, Defol, De-Fol-Ate, Drop-Leaf, Fall, Harvest-Aid, Kusatol, Leafex, and Tumbleaf.

Its use as a herbicide outside the EU remains unaffected, as does its use in other non-herbicidal applications, such as in the production of chlorine dioxide biocides and for pulp and paper bleaching.

Historian James Watson of Massey University in New Zealand wrote a widely reported article, "The Significance of Mr. Richard Buckley's Exploding Trousers"[17][18] about accidents with sodium chlorate when used as a herbicide to control ragwort in the 1930s.