Sodium Chlorate
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Sodium chlorate is an
inorganic compound An inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds⁠that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as ''inorganic chemistry''. Inorgan ...
with the
chemical formula A chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, such as pare ...
Na ClO3. It is a white
crystalline A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macrosc ...
powder that is readily soluble in water. It is
hygroscopic Hygroscopy is the phenomenon of attracting and holding water molecules via either absorption (chemistry), absorption or adsorption from the surrounding Natural environment, environment, which is usually at normal or room temperature. If water mol ...
. It decomposes above 300 °C to release
oxygen Oxygen is a chemical element; it has chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen group (periodic table), group in the periodic table, a highly reactivity (chemistry), reactive nonmetal (chemistry), non ...
and leaves
sodium chloride Sodium chloride , commonly known as Salt#Edible salt, edible salt, is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. It is transparent or translucent, brittle, hygroscopic, and occurs a ...
. Several hundred million tons are produced annually, mainly for applications in
bleach Bleach is the generic name for any chemical product that is used industrially or domestically to remove color from (i.e. to whiten) fabric or fiber (in a process called bleaching) or to disinfect after cleaning. It often refers specifically t ...
ing pulp to produce high brightness
paper Paper is a thin sheet material produced by mechanically or chemically processing cellulose fibres derived from wood, Textile, rags, poaceae, grasses, Feces#Other uses, herbivore dung, or other vegetable sources in water. Once the water is dra ...
.


Synthesis

Industrially, sodium chlorate is produced by the
electrolysis In chemistry and manufacturing, electrolysis is a technique that uses Direct current, direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of c ...
of concentrated sodium chloride solutions. All other processes are obsolete. The sodium chlorate process is not to be confused with the
chloralkali process The chloralkali process (also chlor-alkali and chlor alkali) is an industrial process for the electrolysis of sodium chloride (NaCl) solutions. It is the technology used to produce chlorine and sodium hydroxide (caustic soda), which are commodi ...
, which is an industrial process for the electrolytic production of sodium hydroxide and chlorine gas. The overall reaction can be simplified to the equation: First,
chloride The term chloride refers to a compound or molecule that contains either a chlorine anion (), which is a negatively charged chlorine atom, or a non-charged chlorine atom covalently bonded to the rest of the molecule by a single bond (). The pr ...
is oxidised to form intermediate hypochlorite, ClO, which undergoes further oxidation to chlorate along two competing reaction paths: (1) Anodic chlorate formation at the boundary layer between the electrolyte and the anode, and (2) Autoxidation of hypochlorite in the bulk electrolyte. 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 evolved chlorine does not escape as a gas but undergoes hydrolysis: The hydrolysis of chlorine is considered to be fast. The formation of H+ ions should make the boundary layer at the anode strongly acidic and this is observed at low chloride concentrations. However, large concentrations of chloride, as they occur in industrial chlorate cells, shift the hydrolysis equilibrium to the left. At the boundary layer the concentration of H+ is not high enough to permit diffusion into the bulk electrolyte. Therefore hydrogen is transported away from the anode mostly as hypochlorous acid rather than H+. The hypochlorous acid dissociates in the bulk electrolyte where the pH is high and the hypochlorite ion diffuses back to the anode. More than two thirds of the hypochlorite is consumed by buffering before reaching 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. The hypochlorite then reacts with the rest of the acid: In addition to anode distance the autoxidation also depends on temperature and pH. A typical cell operates at temperatures between 80 °C and 90 °C and at a pH of 6.1–6.4. Independent of the reaction route the discharge of 6 mol of chloride is required to yield 1 mol of chlorate. However, the anodic oxidation route requires 50% additional electric energy. Therefore, industrial cells are optimised to favour autoxidation. Chlorate formation at the anode is treated as a loss reaction and is minimised by design. Other loss reactions also decrease the current efficiency and must be suppressed in industrial systems. The main loss occurs by the back reduction of hypochlorite at the cathode. The reaction is suppressed by the addition of a small amount of dichromate (1–5 g/L) to the electrolyte. A porous film of chromium hydroxide is formed by cathodic deposition. The film impedes the diffusion of anions to the cathode, whereas the access of cations and their reduction is facilitated. The film stops growing on its own after it reaches a certain thickness.


Uses

The main commercial use for sodium chlorate is for making
chlorine dioxide Chlorine dioxide is a chemical compound with the formula ClO2 that exists as yellowish-green gas above 11 °C, a reddish-brown liquid between 11 °C and −59 °C, and as bright orange crystals below −59 °C. It is usually ...
(ClO2). The largest application of ClO2, which accounts for about 95% of the use of chlorate, is in bleaching of pulp. All other, less important
chlorate Chlorate is the common name of the anion, whose chlorine atom is in the +5 oxidation state. The term can also refer to chemical compounds containing this anion, with Chlorate#Compounds (salts), chlorates being the salt (chemistry), salts of chlo ...
s are derived from sodium chlorate, usually by salt metathesis with the corresponding chloride. All
perchlorate A perchlorate is a chemical compound containing the perchlorate ion, , the conjugate base of perchloric acid (ionic perchlorate). As counterions, there can be metal cations, quaternary ammonium cations or other ions, for example, nitronium cat ...
compounds are produced industrially by the oxidation of solutions of sodium chlorate by electrolysis.


Herbicides

Sodium chlorate is used as a non-selective
herbicide Herbicides (, ), also commonly known as weed killers, are substances used to control undesired plants, also known as weeds.EPA. February 201Pesticides Industry. Sales and Usage 2006 and 2007: Market Estimates. Summary in press releasMain page f ...
. It is considered phytotoxic to all green plant parts. It can also kill through root absorption. Sodium chlorate may be used to control a variety of plants including
morning glory Morning glory (also written as morning-glory) is the common name for over 1,000 species of flowering plants in the family Convolvulaceae, whose taxonomy and systematics remain in flux. These species are distributed across numerous genus, gene ...
,
canada thistle ''Cirsium arvense'' is a perennial species of flowering plant in the family Asteraceae, native throughout Europe and western Asia, northern Africa and widely introduced elsewhere.Joint Nature Conservation Committee''Cirsium arvense'' The standa ...
, johnson grass,
bamboo Bamboos are a diverse group of mostly evergreen perennial plant, perennial flowering plants making up the subfamily (biology), subfamily Bambusoideae of the grass family Poaceae. Giant bamboos are the largest members of the grass family, in th ...
, 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. Sodium chlorate is also used as a
defoliant A defoliant is any herbicidal chemical sprayed or dusted on plants to cause their leaves to fall off. Defoliants are widely used for the selective removal of weeds in managing croplands and lawns. Worldwide use of defoliants, along with the d ...
and
desiccant A desiccant is a hygroscopic substance that is used to induce or sustain a state of dryness (desiccation) in its vicinity; it is the opposite of a humectant. Commonly encountered pre-packaged desiccants are solids that absorb water. Desiccant ...
for: *
Corn Maize (; ''Zea mays''), also known as corn in North American English, is a tall stout Poaceae, grass that produces cereal grain. It was domesticated by indigenous peoples of Mexico, indigenous peoples in southern Mexico about 9,000 years ago ...
*
Cotton Cotton (), first recorded in ancient India, is a soft, fluffy staple fiber that grows in a boll, or protective case, around the seeds of the cotton plants of the genus '' Gossypium'' in the mallow family Malvaceae. The fiber is almost pure ...
*Dry beans *
Flax Flax, also known as common flax or linseed, is a flowering plant, ''Linum usitatissimum'', in the family Linaceae. It is cultivated as a food and fiber crop in regions of the world with temperate climates. In 2022, France produced 75% of t ...
*Grain
sorghum ''Sorghum bicolor'', commonly called sorghum () and also known as great millet, broomcorn, guinea corn, durra, imphee, jowar, or milo, is a species in the Poaceae, grass genus ''Sorghum (genus), Sorghum'' cultivated for its grain. The grain i ...
* Peppers *
Rice Rice is a cereal grain and in its Domestication, domesticated form is the staple food of over half of the world's population, particularly in Asia and Africa. Rice is the seed of the grass species ''Oryza sativa'' (Asian rice)—or, much l ...
*
Safflower Safflower (''Carthamus tinctorius'') is a highly branched, herbaceous, thistle-like annual plant in the family Asteraceae. It is one of the world's oldest crops; today, it is commercially cultivated for vegetable oil extracted from the seeds. ...
*Southern peas *
Soybean The soybean, soy bean, or soya bean (''Glycine max'') is a species of legume native to East Asia, widely grown for its edible bean. Soy is a staple crop, the world's most grown legume, and an important animal feed. Soy is a key source o ...
s *
Sunflower The common sunflower (''Helianthus annuus'') is a species of large annual forb of the daisy family Asteraceae. The common sunflower is harvested for its edible oily seeds, which are often eaten as a snack food. They are also used in the pr ...
s If used in combination with
atrazine Atrazine ( ) is a Organochlorine compound, chlorinated herbicide of the triazine class. It is used to prevent pre-emergence broadleaf weeds in crops such as maize (corn), soybean and sugarcane and on turf, such as golf courses and residential law ...
, it increases the persistence of the effect. If used in combination with 2,4-D, performance is improved. Sodium chlorate has a soil sterilant effect. Mixing with other herbicides in aqueous solution is possible to some extent, so long as they are not susceptible to oxidation. 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.


Chemical oxygen generation

Chemical oxygen generators, such as those in commercial aircraft, provide emergency oxygen to passengers to protect them from drops in cabin pressure. Oxygen is generated by high-temperature decomposition of sodium chlorate: Heat required to initiate this reaction is generated by
oxidation Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
of a small amount of iron powder mixed with the sodium chlorate, and the reaction consumes less oxygen than is produced.
Barium peroxide Barium peroxide is an inorganic compound with the formula . This white solid (gray when impure) is one of the most common inorganic peroxides, and it was the first peroxide compound discovered. Being an oxidizer and giving a vivid green colour upo ...
( Ba O2) is used to absorb the
chlorine Chlorine is a chemical element; it has Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between ...
that is a minor product in the decomposition. An ignitor charge is activated by pulling on the emergency mask. Similarly, the Solidox welding system used pellets of sodium chlorate mixed with combustible fibers to generate oxygen.


Oxygenless combustion

Sodium chlorate can be mixed with sucrose sugar to make a highly energetic fuel, similar to that of
gunpowder Gunpowder, also commonly known as black powder to distinguish it from modern smokeless powder, is the earliest known chemical explosive. It consists of a mixture of sulfur, charcoal (which is mostly carbon), and potassium nitrate, potassium ni ...
, that burns in airtight spaces. This is the reaction: However this sodium chlorate is mostly replaced by
potassium chlorate Potassium chlorate is the inorganic compound with the molecular formula KClO3. In its pure form, it is a white solid. After sodium chlorate, it is the second most common chlorate in industrial use. It is a strong oxidizing agent and its most impor ...
.


Organic synthesis

Sodium chlorate can be used with
hydrochloric acid Hydrochloric acid, also known as muriatic acid or spirits of salt, is an aqueous solution of hydrogen chloride (HCl). It is a colorless solution with a distinctive pungency, pungent smell. It is classified as a acid strength, strong acid. It is ...
(or also
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid (English in the Commonwealth of Nations, Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen, ...
and
sodium chloride Sodium chloride , commonly known as Salt#Edible salt, edible salt, is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. It is transparent or translucent, brittle, hygroscopic, and occurs a ...
, the reaction of which generates HCl) to chlorinate aromatic compounds without the use of organic solvents. 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. When combined with a vanadium pentoxide catalyst, it serves as an oxidant for a variety of organic compounds. Examples include the oxidation of
hydroquinone Hydroquinone, also known as benzene-1,4-diol or quinol, is an aromatic organic compound that is a type of phenol, a derivative of benzene, having the chemical formula C6H4(OH)2. It has two hydroxyl groups bonded to a benzene ring in a ''para' ...
to
quinone The quinones are a class of organic compounds that are formally "derived from aromatic compounds benzene.html" ;"title="uch as benzene">uch as benzene or naphthalene] by conversion of an even number of –CH= groups into –C(=O)– groups with ...
, and of furfural to a mixture of maleic and
fumaric acid Fumaric acid or ''trans''-butenedioic acid is an organic compound with the formula HO2CCH=CHCO2H. A white solid, fumaric acid occurs widely in nature. It has a fruit-like taste and has been used as a food additive. Its E number is E297. The sa ...
.


Toxicity in humans

Sodium chlorate is toxic: "doses of a few grams of chlorate are lethal". (ld50 oral in rat
1200mg
kg) The oxidative effect on
hemoglobin Hemoglobin (haemoglobin, Hb or Hgb) is a protein containing iron that facilitates the transportation of oxygen in red blood cells. Almost all vertebrates contain hemoglobin, with the sole exception of the fish family Channichthyidae. Hemoglobin ...
leads to methaemoglobin formation, which is followed by denaturation of the
globin The globins are a superfamily of heme-containing globular proteins, involved in binding and/or transporting oxygen. These proteins all incorporate the globin fold, a series of eight alpha helical segments. Two prominent members include myo ...
protein and a
cross-link In chemistry and biology, a cross-link is a bond or a short sequence of bonds that links one polymer chain to another. These links may take the form of covalent bonds or ionic bonds and the polymers can be either synthetic polymers or natural ...
ing of
erythrocyte Red blood cells (RBCs), referred to as erythrocytes (, with -''cyte'' translated as 'cell' in modern usage) in academia and medical publishing, also known as red cells, erythroid cells, and rarely haematids, are the most common type of blood ce ...
membrane proteins with resultant damage to the membrane enzymes. This leads to increased permeability of the membrane, and severe
hemolysis Hemolysis or haemolysis (), also known by #Nomenclature, several other names, is the rupturing (lysis) of red blood cells (erythrocytes) and the release of their contents (cytoplasm) into surrounding fluid (e.g. blood plasma). Hemolysis may ...
. The denaturation of hemoglobin overwhelms the capacity of the G6PD
metabolic pathway In biochemistry, a metabolic pathway is a linked series of chemical reactions occurring within a cell (biology), cell. The reactants, products, and Metabolic intermediate, intermediates of an enzymatic reaction are known as metabolites, which are ...
. In addition, this enzyme is directly denatured by chlorate. Acute severe hemolysis results, with multi-organ failure, including DIC and
kidney failure Kidney failure, also known as renal failure or end-stage renal disease (ESRD), is a medical condition in which the kidneys can no longer adequately filter waste products from the blood, functioning at less than 15% of normal levels. Kidney fa ...
. In addition there is a direct toxicity to the
proximal renal tubule The proximal tubule is the segment of the nephron in kidneys which begins from the renal (tubular) pole of the Bowman's capsule to the beginning of loop of Henle. At this location, the glomerular parietal epithelial cells (PECs) lining bowman’s ...
. The treatment will consist of exchange transfusion, peritoneal dialysis or
hemodialysis Hemodialysis, American and British English spelling differences#ae and oe, also spelled haemodialysis, or simply ''"'dialysis'"'', is a process of filtering the blood of a person whose kidneys are not working normally. This type of Kidney dialys ...
.


Formulations

Sodium chlorate comes in
dust Dust is made of particle size, fine particles of solid matter. On Earth, it generally consists of particles in the atmosphere that come from various sources such as soil lifted by wind (an aeolian processes, aeolian process), Types of volcan ...
, spray and granule formulations. Mixtures of chlorates and organic compounds pose a severe risk of explosions Marketed formulations contain a
fire retardant A fire retardant is a substance that is used to slow down or stop the spread of fire or reduce its intensity. This is commonly accomplished by chemical reactions that reduce the flammability of fuels or delay their combustion. Fire retardants ...
. Most commercially available chlorate weedkillers contain approximately 53% sodium chlorate with the balance being a fire depressant such as
sodium metaborate Sodium metaborate is a chemical compound of sodium, boron, and oxygen with formula . However, the metaborate ion is trimeric in the anhydrous solid, therefore a more correct formula is or . The formula can be written also as to highlight the re ...
or ammonium phosphates.


Trade names

Sodium chlorate is the active ingredient in a variety of commercial herbicides. Some trade names for products containing sodium chlorate include Atlacide, Defol, De-Fol-Ate, Drop-Leaf, Fall, Harvest-Aid, Kusatol, Leafex, and Tumbleaf. The compound may be used in combination with other herbicides such as atrazine, 2,4-D, bromacil, diuron, and sodium metaborate. Sodium chlorate was an extensively used weed killer within the EU, until 2009 when it was withdrawn after a decision made under terms of EU Regulations. 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.


Cultural references

Historian James Watson of
Massey University Massey University () is a Public university, public research university in New Zealand that provides internal and distance education. The university has campuses in Auckland, Palmerston North, and Wellington. Data from Universities New Zealand ...
in New Zealand wrote a widely reported article, "The Significance of Mr. Richard Buckley's Exploding Trousers" about accidents with sodium chlorate when used as a herbicide to control ragwort in the 1930s. This later won him an Ig Nobel Prize in 2005,James Watson for "The Significance of Mr. Richard Buckley’s Exploding Trousers."
improbable.com
and was the basis for the May 2006 "Exploding Pants" episode of
MythBusters ''MythBusters'' is a science entertainment television series created by Peter Rees (producer), Peter Rees and produced by Beyond International in Australia. The series premiered on the Discovery Channel on January 23, 2003. It was broadcast in ...
.


See also

* Sodium chlorite (NaClO2) *
Sodium chloride Sodium chloride , commonly known as Salt#Edible salt, edible salt, is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. It is transparent or translucent, brittle, hygroscopic, and occurs a ...
(NaCl)


References


Further reading

*"Chlorate de potassium. Chlorate de sodium", ''Fiche toxicol. n° 217'', Paris:Institut national de recherche et de sécurité, 2000. 4pp.


External links


International Chemical Safety Card 1117
{{DEFAULTSORT:Sodium Chlorate Chlorates Sodium compounds Desiccants Pyrotechnic oxidizers Oxidizing agents