Sodium dichromate

Sodium dichromate
Names
	IUPAC name Sodium dichromate
	Other names Chromic acid disodium salt
Identifiers
CAS Number	10588-01-9 ; 7789-12-0 (dihydrate) ;
3D model (JSmol)	Interactive image;
ChEBI	CHEBI:39483 ;
ChemSpider	23723 ;
ECHA InfoCard	100.031.070
EC Number	234-190-3;
PubChem CID	25408;
RTECS number	HX7750000; HX7750000 (dihydrate);
UNII	C9G6VY6ZZ4 ;
UN number	3288
CompTox Dashboard (EPA)	DTXSID8021274 ;
	InChI InChI=1S/2Cr.2Na.7O/q;;2+1;;;;;;2-1 Key: KIEOKOFEPABQKJ-UHFFFAOYSA-N ; InChI=1/2Cr.2Na.7O/q;;2+1;;;;;;2-1/rCr2O7.2Na/c3-1(4,5)9-2(6,7)8;;/q-2;2*+1 Key: KIEOKOFEPABQKJ-RXLKZJBDAW;
	SMILES [Na+].[Na+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O;
Properties
Chemical formula	Na2Cr2O7
Molar mass	261.97 g/mol (anhydrous); 298.00 g/mol (dihydrate)
Appearance	bright orange
Odor	odorless
Density	2.52 g/cm3
Melting point	356.7 °C (674.1 °F; 629.8 K)
Boiling point	400 °C (752 °F; 673 K) decomposes
Solubility in water	73 g/100 mL at 25 °C
Solubility in other solvents	soluble in methanol, ethanol
Refractive index (nD)	1.661 (dihydrate)
Hazards
Safety data sheet	ICSC 1369
EU classification (DSD) (outdated)	Oxidant (O); Carc. Cat. 2; Muta. Cat. 2; Repr. Cat. 2; Very toxic (T+); Harmful (Xn); Corrosive (C); Dangerous for the environment (N)
R-phrases (outdated)	R45, R46, R60, R61, R8, R21, R25, R26, R34, R42/43, R48/23, R50/53,
S-phrases (outdated)	S53, S45, S60, S61
NFPA 704 (fire diamond)	0 4 1 OX
	Lethal dose or concentration (LD, LC):
LD50 (median dose)	50 mg/kg
Related compounds
Other anions	Sodium chromate; Sodium molybdate; Sodium tungstate
Other cations	Potassium dichromate; Ammonium dichromate
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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	Infobox references

Sodium dichromate is the inorganic compound with the formula Na₂ Cr₂ O₇. Usually, however, the salt is handled as its dihydrate Na₂Cr₂O₇·2H₂O. Virtually all chromium ore is processed via conversion to sodium dichromate and virtually all compounds and materials based on chromium are prepared from this salt.[1] In terms of reactivity and appearance, sodium dichromate and potassium dichromate are very similar. The sodium salt is, however, around twenty times more soluble in water than the potassium salt (49 g/L at 0 °C) and its equivalent weight is also lower, which is often desirable.[2]

Production

Sodium dichromate is generated on a large scale from ores containing chromium(III) oxides. The ore is fused with a base, typically sodium carbonate, at around 1000 °C in the presence of air (source of oxygen):

${\ce {2Cr2O3 + 4Na2CO3 + 3O2 -> 4Na2CrO4 + 4CO2}}$

This step solubilizes the chromium and allows it to be extracted into hot water. At this stage, other components of the ore such as aluminium and iron compounds, are poorly soluble. Acidification of the resulting aqueous extract with sulfuric acid or carbon dioxide affords the dichromate:

${\ce {2Na2CrO4 + 2CO2 + H2O -> Na2Cr2O7 + 2NaHCO3}}$

${\ce {2Na2CrO4 + H2SO4 -> Na2Cr2O7 + Na2SO4 + H2O}}$

The dichromate is isolated as the dihydrate by crystallization. In this way, many millions of kilograms of sodium dichromate are produced annually.

Since chromium(VI) is toxic, especially as the dust, such factories are subject to stringent regulations. For example, effluent from such refineries is treated with reducing agents to return any chromium(VI) to chromium(III), which is less threatening to the environment.[1] A variety of hydrates of this salt are known, ranging from the decahydrate below 19.5 °C (CAS# 13517-17-4 ) as well as hexa-, tetra-, and dihydrates. Above 62 °C, these salts lose water spontaneously to give the anhydrous material. It is crystallised around 30 to 35 degrees C

Reactions

Dichromate and chromate salts are oxidizing agents. For the tanning of leather, sodium dichromate is first reduced with sulfur dioxide.

In the area of organic synthesis,[2] this compound oxidizes benzylic and allylic C-H bonds to carbonyl derivatives. For example, 2,4,6-trinitrotoluene is oxidized to the corresponding carboxylic acid.[3] Similarly, 2,3-dimethylnaphthalene is oxidized by Na₂Cr₂O₇ to 2,3-naphthalenedicarboxylic acid.[4]

Secondary alcohols are oxidized to the corresponding ketone, e.g. menthol to menthone;[5] dihydrocholesterol to cholestanone:[6]

3 R₂CHOH + Cr₂O₇²⁻ + 2 H⁺ → 3 R₂C=O + Cr₂O₃ + 4 H₂O

Relative to the potassium salt, the main advantage of sodium dichromate is its greater solubility in water and polar solvents like acetic acid.

Sodium dichromate can be used in fluorene to fluorenone conversion.

Safety

Like all hexavalent chromium compounds, sodium dichromate is carcinogenic.[7] The compound is also corrosive and exposure may produce severe eye damage or blindness.[8] Human exposure further encompasses impaired fertility, heritable genetic damage and harm to unborn children.

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References

Gerd Anger, Jost Halstenberg, Klaus Hochgeschwender, Christoph Scherhag, Ulrich Korallus, Herbert Knopf, Peter Schmidt, Manfred Ohlinger, "Chromium Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. doi:10.1002/14356007.a07_067
Freeman, F. "Sodium Dichromate" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. doi:10.1002/047084289.
Clarke, H. T.; Hartman, W. W. (1941). "2,4,6-Trinitrobenzoic Acid". Organic Syntheses.CS1 maint: multiple names: authors list (link); Collective Volume, 1, p. 543
Friedman, L. (1973). "2,3-Naphthalenedicarboxylic Acid". Organic Syntheses.; Collective Volume, 5, p. 810
L. T. Sandborn (1929). "l-Menthone". Organic Syntheses. 9: 59.; Collective Volume, 1, p. 340
W. F. Bruce (1941). "Cholestanone". Organic Syntheses.; Collective Volume, 2, p. 139
IARC (2012) [17-24 March 2009]. Volume 100C: Arsenic, Metals, Fibres, and Dusts (PDF). Lyon: International Agency for Research on Cancer. ISBN 978-92-832-0135-9. Retrieved 2020-01-05. There is sufficient evidence in humans for the carcinogenicity of chromium (VI) compounds. Chromium (VI) compounds cause cancer of the lung. Also positive associations have been observed between exposure to Chromium (VI) compounds and cancer of the nose and nasal sinuses. There is sufficient evidence in experimental animals for the carcinogenicity of chromium (VI) compounds. Chromium (VI) compounds are carcinogenic to humans (Group 1).
ILO 1369 - Sodium Dichromate

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[Ullmann-1] Gerd Anger, Jost Halstenberg, Klaus Hochgeschwender, Christoph Scherhag, Ulrich Korallus, Herbert Knopf, Peter Schmidt, Manfred Ohlinger, "Chromium Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. doi:10.1002/14356007.a07_067

[eEROS-2] Freeman, F. "Sodium Dichromate" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. doi:10.1002/047084289.

[cv1p0543-3] Clarke, H. T.; Hartman, W. W. (1941). "2,4,6-Trinitrobenzoic Acid". Organic Syntheses.CS1 maint: multiple names: authors list (link); Collective Volume, 1, p. 543

[4] Friedman, L. (1973). "2,3-Naphthalenedicarboxylic Acid". Organic Syntheses.; Collective Volume, 5, p. 810

[5] L. T. Sandborn (1929). "l-Menthone". Organic Syntheses. 9: 59.; Collective Volume, 1, p. 340

[6] W. F. Bruce (1941). "Cholestanone". Organic Syntheses.; Collective Volume, 2, p. 139

[book100C-7] IARC (2012) [17-24 March 2009]. Volume 100C: Arsenic, Metals, Fibres, and Dusts (PDF). Lyon: International Agency for Research on Cancer. ISBN 978-92-832-0135-9. Retrieved 2020-01-05. There is sufficient evidence in humans for the carcinogenicity of chromium (VI) compounds. Chromium (VI) compounds cause cancer of the lung. Also positive associations have been observed between exposure to Chromium (VI) compounds and cancer of the nose and nasal sinuses. There is sufficient evidence in experimental animals for the carcinogenicity of chromium (VI) compounds. Chromium (VI) compounds are carcinogenic to humans (Group 1).

[8] ILO 1369 - Sodium Dichromate