Sodium chlorate

Sodium chlorate is an inorganic compound with the chemical

formula NaClO3 . It is a white crystalline powder that is readily
Sodium chlorate
soluble in water. It is hygroscopic. It decomposes above 300 °C
to release oxygen[4] and leaves sodium chloride. Several
hundred million tons are produced annually, mainly for
applications in bleaching pulp to produce high brightness
paper.[7]

Contents
Synthesis
Uses
Herbicides
Chemical oxygen generation
Oxygenless combustion
Organic synthesis
Toxicity in humans
Formulations
Trade names
Cultural references
See also
References
Further reading
External links
Unit cell of sodium chlorate
Names
Synthesis IUPAC name
Sodium chlorate
Industrially, sodium chlorate is produced by the electrolysis of
concentrated sodium chloride solutions. All other processes are Other names
obsolete. The sodium chlorate process is not to be confused with Sodium chlorate(V)
the chloralkali process, which is an industrial process for the Identifiers
electrolytic production of sodium hydroxide and chlorine gas.
CAS Number 7775-09-9 (https://co
The overall reaction can be simplified to the equation: mmonchemistry.cas.
org/detail?cas_rn=77
NaCl + 3 H2 O → NaClO3 + 3 H2
75-09-9) 

First, chloride is oxidised to form intermediate hypochlorite, 3D model Interactive image (htt
ClO−, which undergoes further oxidisation to chlorate along two (JSmol) ps://chemapps.stolaf.
competing reaction paths: (1) Anodic chlorate formation at the
boundary layer between the electrolyte and the anode, and (2) edu/jmol/jmol.php?m
Autoxidation of hypochlorite in the bulk electrolyte. odel=%5BNa%2B%5
D.%5BO-%5DCl%2
Under electrolysis hydrogen and sodium hydroxide are formed
8%3DO%29%3DO)
at the cathode and chloride ions are discharged at the anode
(mixed metal oxide electrode is often used). The evolved ChEBI CHEBI:65242 (http
chlorine does not escape as a gas but undergoes hydrolysis: s://www.ebi.ac.uk/ch
ebi/searchId.do?che
Cl2 + H2 O ⇋ HClO + H+ + Cl−
biId=65242) 

The hydrolysis of chlorine is considered to be fast. The ChemSpider 22895 (https://www.c

formation of H+ ions should make the boundary layer at the hemspider.com/Che
anode strongly acidic and this is observed at low chloride mical-Structure.2289
concentrations. However, large concentrations of chloride, as 5.html) 
they occur in industrial chlorate cells, shift the hydrolysis
equilibrium to the left. At the boundary layer the concentration ECHA InfoCard 100.028.989 (https://
of H+ is not high enough to permit diffusion into the bulk echa.europa.eu/subs
electrolyte. Therefore hydrogen is transported away from the tance-information/-/s
anode mostly as hypochlorous acid rather than H+. The ubstanceinfo/100.02
hypochlorous acid dissociates in the bulk electrolyte where the 8.989)
pH is high and the hypochlorite ion diffuses back to the anode. EC Number 231-887-4
More than two thirds of the hypochlorite is consumed by
buffering before reaching the anode. The remainder is KEGG C18765 (https://www.
discharged at the anode to form chlorate and oxygen: kegg.jp/entry/C1876
5) 
3 ClO− + 1.5 H2 O → ClO3 − + 3 H+ + 2 Cl− + 0.75 O2
MeSH Sodium+chlorate (htt
The autoxidation of hypochlorous acid in the bulk electrolyte ps://www.nlm.nih.go
proceeds according to the simplified overall equation: v/cgi/mesh/2014/MB
_cgi?mode=&term=S
3 HClO → ClO3 − + 2 Cl− + 3 H+ odium+chlorate)

It is preceded by the dissociation of a part of the hypochlorous PubChem CID 516902 (https://pubc
acid involved: hem.ncbi.nlm.nih.go
v/compound/516902)
HClO → ClO− + H+
RTECS FO0525000
The reaction requires a certain distance from the anode to occur number
to a significant degree, where the electrolyte is sufficiently UNII T95DR77GMR (http
buffered by the hydroxyl formed at the cathode. The
s://fdasis.nlm.nih.go
hypochlorite then reacts with the rest of the acid:
v/srs/srsdirect.jsp?re
2 HClO + ClO− → ClO3 − + 2 Cl− + 2 H+ gno=T95DR77GMR) 

In addition to anode distance the autoxidation also depends on UN number 1495, 2428
temperature and pH. A typical cell operates at temperatures
CompTox DTXSID7026025 (htt
between 80 °C and 90 °C and at a pH of 6.1–6.4.
Dashboard ps://comptox.epa.go
(EPA)
Independent of the reaction route the discharge of 6  mol of v/dashboard/chemic
chloride is required to yield 1  mol of chlorate. However, the al/details/DTXSID702
anodic oxidation route requires 50% additional electric energy. 6025)

InChI
Therefore, industrial cells are optimised to favour autoxidation. InChI=1S/ClHO3.Na/c2-1(3)4;/h(H,2,
Chlorate formation at the anode is treated as a loss reaction and 3,4);/q;+1/p-1 
is minimised by design. Key: YZHUMGUJCQRKBT-UHFFFAO
YSA-M  
Other loss reactions also decrease the current efficiency and
InChI=1S/ClHO3.Na/c2-1(3)4;/h(H,2,
must be suppressed in industrial systems. The main loss occurs 3,4);/q;+1/p-1
by the back reduction of hypochlorite at the cathode. The Key: YZHUMGUJCQRKBT-UHFFFAO
reaction is suppressed by the addition of a small amount of YSA-M
dichromate (1–5  g/L) to the electrolyte. A porous film of
InChI=1/ClHO3.Na/c2-1(3)4;/h(H,2,3,
chromium hydroxide is formed by cathodic deposition. The film 4);/q;+1/p-1
impedes the diffusion of anions to the cathode, whereas the Key: YZHUMGUJCQRKBT-REWHXW
access of cations and their reduction is facilitated. The film stops OFAH
growing on its own after it reaches a certain thickness.[7]
SMILES
[Na+].[O-]Cl(=O)=O
Uses
Properties
The main commercial use for sodium chlorate is for making Chemical NaClO3
chlorine dioxide (ClO2 ). The largest application of ClO2 , which formula
accounts for about 95% of the use of chlorate, is in bleaching of Molar mass 106.44 g mol−1
pulp. All other, less important chlorates are derived from sodium
Appearance Colorless or white
chlorate, usually by salt metathesis with the corresponding
chloride. All perchlorate compounds are produced industrially solid, hygroscopic
by the oxidation of solutions of sodium chlorate by Odor Odorless
electrolysis.[7] Density 2.49 g/cm3 (15 °C)[1]
2.54 g/cm3
Herbicides (20.2 °C)[2]
Melting point 248–261 °C (478–
Sodium chlorate is used as a non-selective herbicide. It is 502 °F; 521–534 K)
considered phytotoxic to all green plant parts. It can also kill
Boiling point 300–400 °C (572–
through root absorption.
752 °F; 573–673 K)
Sodium chlorate may be used to control a variety of plants decomposes[1]
including morning glory, canada thistle, johnson grass, bamboo, Solubility in 79 g/100 mL (0 °C)
Ragwort, and St John's wort. The herbicide is mainly used on water 89 g/100 mL (10 °C)
non-crop land for spot treatment and for total vegetation control 105.7 g/100 mL
on areas including roadsides, fenceways, and ditches. Sodium
(25 °C)
chlorate is also used as a defoliant and desiccant for:
125 g/100 mL
Corn Rice (40 °C)
Cotton Safflower 220.4 g/100 mL
Dry beans Southern peas (100 °C)[3]
Flax Soybeans Solubility Soluble in glycerol,
Grain sorghum Sunflowers hydrazine, methanol
Peppers Slightly soluble in
ethanol, ammonia[1]
If used in combination with atrazine, it increases the persistence Solubility in Sparingly soluble[1]
of the effect. If used in combination with 2,4-D, performance is
acetone
improved. Sodium chlorate has a soil sterilant effect. Mixing
with other herbicides in aqueous solution is possible to some Solubility in 20 g/100 g
extent, so long as they are not susceptible to oxidation. glycerol (15.5 °C)[1]
The sale of sodium chlorate as a weedkiller was banned in the Solubility in 14.7 g/100 g[1]
European Union in 2009 citing health dangers, with existing ethanol
stocks to be used within the following year.[8]
Vapor pressure <0.35 mPa[2]
Magnetic −34.7·10−6 cm3/mol
Chemical oxygen generation susceptibility
(χ)
Chemical oxygen generators, such as those in commercial Refractive 1.515 (20 °C)[4]
aircraft, provide emergency oxygen to passengers to protect index (nD)
them from drops in cabin pressure. Oxygen is generated by
Structure[5]
high-temperature decomposition of sodium chlorate:[9]
Crystal cubic
2 NaClO3 → 2 NaCl + 3 O2 structure
Point group P213
Heat required to initiate this reaction is generated by oxidation
Lattice a = 6.57584 Å
of a small amount of iron powder mixed with the sodium constant
chlorate, and the reaction consumes less oxygen than is
produced. Barium peroxide (BaO2 ) is used to absorb the Formula units 4
(Z)
chlorine that is a minor product in the decomposition.[10] An
ignitor charge is activated by pulling on the emergency mask. Thermochemistry
Similarly, the Solidox welding system used pellets of sodium Heat capacity 104.6 J/mol·K[1]
chlorate mixed with combustible fibers to generate oxygen. (C)
Std molar 129.7 J/mol·K[1]
entropy
Oxygenless combustion (S ⦵298)
Sodium chlorate can be mixed with sucrose sugar to make a Std enthalpy of -365.4 kJ/mol[1]
highly explosive fuel, similar to that of gunpowder, that burns in formation
airtight spaces. This is the reaction: (Δ f H ⦵298)
Gibbs free -275 kJ/mol[1]
8 NaClO3 + C12 H22 O11 → 8 NaCl + 12 CO2 + 11 energy
H2 O (Δ f G⦵)

However this sodium chlorate is mostly replaced by potassium Hazards

chlorate. GHS labelling:
Pictograms
Organic synthesis

Sodium chlorate can be used with hydrochloric acid (or also [6]

sulfuric acid and sodium chloride, the reaction of which

generates HCl) to chlorinate aromatic compounds without the Signal word Danger
use of organic solvents. In this case its function is to oxidize the
Hazard H271, H302, H411[6]
HCl to obtain either HOCl or Cl2 (depending upon the pH) in- statements
situ which are the active chlorinating agents.[11]
Precautionary P220, P273[6]
statements
Toxicity in humans NFPA 704
(fire diamond) 0
Sodium chlorate is toxic: "doses of a few grams of chlorate are 2 3
lethal".[7] (ld50 oral in rats 1200mg (https://fscimage.fishersci.co OX
m/msds/21100.htm)/kg) The oxidative effect on hemoglobin
Flash point Non-flammable
leads to methaemoglobin formation, which is followed by Lethal dose or concentration (LD,
denaturation of the globin protein and a cross-linking of LC):
erythrocyte membrane proteins with resultant damage to the
LD50 (median 600 mg/kg (rats,
membrane enzymes. This leads to increased permeability of the
dose) oral)
membrane, and severe hemolysis. The denaturation of
hemoglobin overwhelms the capacity of the G6PD metabolic 700 mg/kg (dogs,
pathway. In addition, this enzyme is directly denatured by oral)[1]
chlorate. Safety data ICSC 1117 (http://ww
sheet (SDS) w.inchem.org/docum
Acute severe hemolysis results, with multi-organ failure,
ents/icsc/icsc/eics11
including DIC and kidney failure. In addition there is a direct
17.htm)
toxicity to the proximal renal tubule.[12] The treatment will
consist of exchange transfusion, peritoneal dialysis or Related compounds
hemodialysis.[13] Other anions Sodium chloride
Sodium hypochlorite
Formulations Sodium chlorite
Sodium perchlorate
Sodium chlorate comes in dust, spray and granule formulations. Sodium bromate
Mixtures of chlorates and organic compounds pose a severe risk Sodium iodate
of explosions[14]
Other cations Ammonium chlorate
Marketed formulations contain a fire retardant. Most Potassium chlorate
commercially available chlorate weedkillers contain Barium chlorate
approximately 53% sodium chlorate with the balance being a Related Chloric acid
fire depressant such as sodium metaborate or ammonium compounds
phosphates. Except where otherwise noted, data
are given for materials in their
Trade names standard state (at 25 °C [77 °F],
100 kPa).

Sodium chlorate is the active ingredient in a variety of  verify (what is   ?)

commercial herbicides. Some trade names for products Infobox references
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 in New Zealand wrote a widely reported article, "The
Significance of Mr. Richard Buckley's Exploding Trousers"[15][16] about accidents with sodium chlorate
when used as a herbicide to control ragwort in the 1930s.[17] This later won him an Ig Nobel Prize in
2005,[18] and was the basis for the May 2006 "Exploding Pants" episode of MythBusters.

See also
Sodium chloride

References
1. "Sodium chlorate" (http://chemister.ru/Database/properties-en.php?dbid=1&id=786).
2. "GPS Safety Summary of Sodium Chlorate" (http://www.arkema.com/export/shared/.content/
media/downloads/socialresponsability/safety-summuries/safety-summaries-hydrogen-peroxi
de-sodium-chlorate-2012-06-30.pdf) (PDF). arkema.com. Arkema. Retrieved 2014-05-25.
3. Seidell, Atherton; Linke, William F. (1952). Solubilities of Inorganic and Organic Compounds.
Van Nostrand.
4. CID 516902 (https://pubchem.ncbi.nlm.nih.gov/compound/516902) from PubChem
5. S. C. Abrahams, J. L. Bernstein (1977). "Remeasurement of Optically Active NaClO3 and
NaBrO3" (https://doi.org/10.1107%2FS0567740877011637). Acta Crystallographica. B33
(11): 3601–3604. doi:10.1107/S0567740877011637 (https://doi.org/10.1107%2FS05677408
77011637).
6. Sigma-Aldrich Co., Sodium chlorate (https://www.sigmaaldrich.com/US/en/product/sigald/40
3016). Retrieved on 2022-02-21.
7. Vogt, Helmut; Balej, Jan; Bennett, John E.; Wintzer, Peter; Sheikh, Saeed Akbar; Gallone,
Patrizio (2000). "Chlorine Oxides and Chlorine Oxygen Acids". Ullmann's Encyclopedia of
Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a06_483 (https://doi.or
g/10.1002%2F14356007.a06_483).
8. "Sodium chlorate banned by EC" (https://www.hortweek.com/sodium-chlorate-banned-ec/fre
sh-produce/article/841864). Horticulture Week. 28 August 2008.
9. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.).
Butterworth-Heinemann. ISBN 978-0-08-037941-8.
10. Yunchang Zhang; Girish Kshirsagar & James C. Cannon (1993). "Functions of Barium
Peroxide in Sodium Chlorate Chemical Oxygen". Ind. Eng. Chem. Res. 32 (5): 966–969.
doi:10.1021/ie00017a028 (https://doi.org/10.1021%2Fie00017a028).
11. Sharma, Sushil Kumar; Agarwal, D. D. (July 2014). "Oxidative Chlorination of Aromatic
Compounds in Aqueous Media" (https://www.ijsrp.org/research-paper-0714/ijsrp-p3182.pdf)
(PDF). International Journal of Scientific and Research Publications. 4 (7). Retrieved
August 23, 2021.
12. Oliver J.; MacDowell M., Tracy A (1951). "The Pathogenesis of Acute Renal Failure
Associated with Traumatic and Toxic Injury. Renal Ischemia, Nephrotoxic Damage and the
Ischemuric Episode 1" (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC441312). J Clin
Invest. 30 (12): 1307–439. doi:10.1172/JCI102550 (https://doi.org/10.1172%2FJCI102550).
PMC 441312 (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC441312). PMID 14897900 (http
s://pubmed.ncbi.nlm.nih.gov/14897900).
13. Goldfrank's Toxicologic Emergencies, McGraw-Hill Professional; 8th edition (March 28,
2006), ISBN 978-0-07-143763-9
14. Beveridge, Alexander (1998). Forensic Investigation of Explosions. Taylor & Francis Ltd.
ISBN 0-7484-0565-8.
15. "The Significance of Mr. Richard Buckley's Exploding Trousers: Reflections on an Aspect of
Technological Change in New Zealand Dairy Farming between the World Wars" (http://aghis
t.metapress.com/content/q3224660874x8q51/) Archived (https://web.archive.org/web/20131
023043832/http://aghist.metapress.com/content/q3224660874x8q51/) 2013-10-23 at the
Wayback Machine, Agricultural History magazine
16. "Histories: Farmer Buckley's exploding trousers" (https://www.newscientist.com/article/mg18
424771.800-histories-farmer-buckleys-exploding-trousers-.html), New Scientist
17. "Trousers Explode (http://paperspast.natlib.govt.nz/cgi-bin/paperspast?a=d&d=EP1933042
1.2.104&e=-------10--1----0--), Evening Post, 21 April 1933
18. James Watson for "The Significance of Mr. Richard Buckley’s Exploding Trousers." (http://im
probable.com/ig/ig-pastwinners.html#ig2005), improbable.com

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 (https://www.cdc.gov/niosh/ipcsneng/neng1117.ht
ml)

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