Chromium trioxide

Last updated
Chromium trioxide
CrO3-from-xtal-1970-bulk-3D-balls.png
   Chromium, Cr
   Oxygen, O
Chromium(VI) oxide.jpg
Names
IUPAC name
Chromium trioxide
Other names
Chromic anhydride, Chromium(VI) oxide, Chromic acid (misnomer)
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.014.189 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
RTECS number
  • GB6650000
UNII
UN number 1463
  • InChI=1S/Cr.3O Yes check.svgY
    Key: WGLPBDUCMAPZCE-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/Cr.3O/rCrO3/c2-1(3)4
    Key: WGLPBDUCMAPZCE-YFSAMUSXAF
  • O=[Cr](=O)=O
Properties
CrO3
Molar mass 99.993 g·mol−1
AppearanceDark red granular solid, deliquescent
Odor Odorless
Density 2.7 g/cm3 (20 °C) [1]
Melting point 197 °C (387 °F; 470 K) [1]
Boiling point 250 °C (482 °F; 523 K)
decomposes [1]
  • 164.8 g/(100 mL) (0 °C)
  • 169 g/(100 mL) (25 °C) [1]
  • 172.6 g/(100 mL) (40 °C)
  • 198.1 g/(100 mL) (100 °C) [2]
Solubility Soluble in H2SO4, HNO3, (CH3CH2)2O, CH3COOH, (CH3)2CO
+40·10−6 cm3/mol [1]
Thermochemistry
Std molar
entropy (S⦵298)
73.2 J/(mol·K) [3]
−589.3 kJ/mol [4]
Hazards
GHS labelling:
GHS-pictogram-rondflam.svg GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg [5]
Danger
H271, H301+H311, H314, H317, H330, H334, H335, H340, H350, H361f, H372, H410 [5]
P210, P260, P280, P303+P361+P353, P304+P340+P310, P305+P351+P338 [5]
NFPA 704 (fire diamond)
[6]
NFPA 704.svgHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 0: Will not burn. E.g. waterInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazard OX: Oxidizer. E.g. potassium perchlorate
4
0
2
OX
Lethal dose or concentration (LD, LC):
80 mg/kg (rats, oral) [6]
Safety data sheet (SDS) ICSC 1194
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Chromium trioxide (also known as chromium(VI) oxide or chromic anhydride) is an inorganic compound with the formula CrO3. It is the acidic anhydride of chromic acid, and is sometimes marketed under the same name. [6] This compound is a dark-purple solid under anhydrous conditions and bright orange when wet. The substance dissolves in water accompanied by hydrolysis.[ clarification needed ] Millions of kilograms are produced annually, mainly for electroplating. [7] Chromium trioxide is a powerful oxidiser, a mutagen, and a carcinogen. [8]

Contents

Production, structure, and basic reactions

Chromium trioxide is generated by treating sodium dichromate with sulfuric acid: [6]

H2SO4 + Na2Cr2O7 → 2 CrO3 + Na2SO4 + H2O

Approximately 100,000 tonnes are produced annually by this or similar routes. [7]

The solid consists of chains of tetrahedrally coordinated chromium atoms that share vertices. Each chromium center therefore shares two oxygen centers with neighbors. Two oxygen atoms are not shared, giving an overall stoichiometry of 1:3. [9] [10]

Ball-and-stick model of chains in the crystal structure of CrO3 Chromium, Cr Oxygen, O CrO3-from-xtal-1970-chain-3D-balls.png
Ball-and-stick model of chains in the crystal structure of CrO3
   Chromium, Cr
   Oxygen, O

The structure of monomeric CrO3 has been calculated using density functional theory, and is predicted to be pyramidal (point group C3v) rather than planar (point group D3h). [11]

CrO3-monomer-from-DFT-PW91-aD-2008-side-3D-balls.png

Chromium trioxide decomposes above 197 °C, liberating oxygen and eventually giving Cr2O3:

4 CrO3 → 2 Cr2O3 + 3 O2

It is used in organic synthesis as an oxidant, often as a solution in acetic acid, [9] or acetone in the case of the Jones oxidation. In these oxidations, the Cr(VI) converts primary alcohols to the corresponding carboxylic acids and secondary alcohols to ketones. The reactions are shown below:

Applications

Chromium trioxide is mainly used in chrome plating. It is typically employed with additives that affect the plating process but do not react with the trioxide. The trioxide reacts with cadmium, zinc, and other metals to generate passivating chromate films that resist corrosion. It is also used in the production of synthetic rubies. Chromic acid solution is also used in applying types of anodic coating to aluminium, which are primarily used in aerospace applications. On the International Space Station, it is used to control bacteria growth in the wastewater storage tank. A chromic acid/phosphoric acid solution is also the preferred stripping agent of anodic coatings of all types.

Safety

Chromium trioxide is highly toxic, corrosive, and carcinogenic. [12] It is the main example of hexavalent chromium, an environmental hazard. [13] The related chromium(III) derivatives are not particularly dangerous; thus, reductants are used to destroy chromium(VI) samples.

Chromium trioxide, being a powerful oxidizer, will ignite organic materials such as alcohols on contact.

Images

Related Research Articles

<span class="mw-page-title-main">Chromium</span> Chemical element, symbol Cr and atomic number 24

Chromium is a chemical element; it has symbol Cr and atomic number 24. It is the first element in group 6. It is a steely-grey, lustrous, hard, and brittle transition metal.

<span class="mw-page-title-main">Oxidizing agent</span> Chemical compound used to oxidize another substance in a chemical reaction

An oxidizing agent is a substance in a redox chemical reaction that gains or "accepts"/"receives" an electron from a reducing agent. In other words, an oxidizer is any substance that oxidizes another substance. The oxidation state, which describes the degree of loss of electrons, of the oxidizer decreases while that of the reductant increases; this is expressed by saying that oxidizers "undergo reduction" and "are reduced" while reducers "undergo oxidation" and "are oxidized". Common oxidizing agents are oxygen, hydrogen peroxide, and the halogens.

Chromic acid is jargon for a solution formed by the addition of sulfuric acid to aqueous solutions of dichromate. It consists at least in part of chromium trioxide.

<span class="mw-page-title-main">Chrome plating</span> Technique of electroplating

Chrome plating is a technique of electroplating a thin layer of chromium onto a metal object. A chrome plated part is called chrome, or is said to have been chromed. The chromium layer can be decorative, provide corrosion resistance, facilitate cleaning, or increase surface hardness. Sometimes, a less expensive substitute for chrome such as nickel may be used for aesthetic purposes.

<span class="mw-page-title-main">Chromate and dichromate</span> Chromium(VI) anions

Chromate salts contain the chromate anion, CrO2−
4. Dichromate salts contain the dichromate anion, Cr
2O2−
7. They are oxyanions of chromium in the +6 oxidation state and are moderately strong oxidizing agents. In an aqueous solution, chromate and dichromate ions can be interconvertible.

An acidic oxide is an oxide that either produces an acidic solution upon addition to water, or acts as an acceptor of hydroxide ions effectively functioning as a Lewis acid. Acidic oxides will typically have a low pKa and may be inorganic or organic. A commonly encountered acidic oxide, carbon dioxide produces an acidic solution when dissolved.

<span class="mw-page-title-main">Potassium dichromate</span> Chemical compound

Potassium dichromate, K2Cr2O7, is a common inorganic chemical reagent, most commonly used as an oxidizing agent in various laboratory and industrial applications. As with all hexavalent chromium compounds, it is acutely and chronically harmful to health. It is a crystalline ionic solid with a very bright, red-orange color. The salt is popular in laboratories because it is not deliquescent, in contrast to the more industrially relevant salt sodium dichromate.

<span class="mw-page-title-main">Pyridinium chlorochromate</span> Chemical compound

Pyridinium chlorochromate (PCC) is a yellow-orange salt with the formula [C5H5NH]+[CrO3Cl]−. It is a reagent in organic synthesis used primarily for oxidation of alcohols to form carbonyls. A variety of related compounds are known with similar reactivity. PCC offers the advantage of the selective oxidation of alcohols to aldehydes or ketones, whereas many other reagents are less selective.

<span class="mw-page-title-main">Sodium dichromate</span> Inorganic compound

Sodium dichromate is the inorganic compound with the formula Na2Cr2O7. However, the salt is usually 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. 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.

<span class="mw-page-title-main">Chromium compounds</span> Chemical compounds containing chromium

Chromium compounds are compounds containing the element chromium (Cr). Chromium is a member of group 6 of the transition metals. The +3 and +6 states occur most commonly within chromium compounds, followed by +2; charges of +1, +4 and +5 for chromium are rare, but do nevertheless occasionally exist.

<span class="mw-page-title-main">Ammonium dichromate</span> Chemical compound

Ammonium dichromate is an inorganic compound with the formula (NH4)2Cr2O7. In this compound, as in all chromates and dichromates, chromium is in a +6 oxidation state, commonly known as hexavalent chromium. It is a salt consisting of ammonium ions and dichromate ions.

<span class="mw-page-title-main">Collins reagent</span> Chemical compound

Collins reagent is the complex of chromium(VI) oxide with pyridine in dichloromethane. This metal-pyridine complex, a red solid, is used to oxidize primary alcohols to the corresponding aldehydes and secondary alcohols to the corresponding ketones. This complex is a hygroscopic orange solid.

<span class="mw-page-title-main">Cornforth reagent</span> Chemical compound

The pyridinium dichromate(PDC) or Cornforth reagent is a pyridinium salt of dichromate with the chemical formula [C5H5NH]2[Cr2O7]. This compound is named after the Australian-British chemist Sir John Warcup Cornforth (b. 1917) who introduced it in 1962. The Cornforth reagent is a strong oxidizing agent which can convert primary and secondary alcohols to aldehydes and ketones respectively. In its chemical structure and functions it is closely related to other compounds made from hexavalent chromium oxide, such as pyridinium chlorochromate and Collins reagent. Because of their toxicity, these reagents are rarely used nowadays.

<span class="mw-page-title-main">Sodium chromate</span> Chemical compound

Sodium chromate is the inorganic compound with the formula Na2CrO4. It exists as a yellow hygroscopic solid, which can form tetra-, hexa-, and decahydrates. It is an intermediate in the extraction of chromium from its ores.

Alcohol oxidation is a collection of oxidation reactions in organic chemistry that convert alcohols to aldehydes, ketones, carboxylic acids, and esters where the carbon carries a higher oxidation state. The reaction mainly applies to primary and secondary alcohols. Secondary alcohols form ketones, while primary alcohols form aldehydes or carboxylic acids.

<span class="mw-page-title-main">Chromium(VI) oxide peroxide</span> Chemical compound

Chromium(VI) oxide peroxide or chromium oxide peroxide or more accurately chromium(VI) oxide diperoxide is an inorganic compound with the chemical formula CrO5 or more accurately CrO(O2)2. It is an unstable dark blue compound. This compound contains one oxo ligand and two peroxo ligands, making a total of five oxygen atoms per chromium atom.

Oxidation with chromium(VI) complexes involves the conversion of alcohols to carbonyl compounds or more highly oxidized products through the action of molecular chromium(VI) oxides and salts. The principal reagents are Collins reagent, PDC, and PCC. These reagents represent improvements over inorganic chromium(VI) reagents such as Jones reagent.

<span class="mw-page-title-main">Jones oxidation</span> Oxidation of alcohol

The Jones oxidation is an organic reaction for the oxidation of primary and secondary alcohols to carboxylic acids and ketones, respectively. It is named after its discoverer, Sir Ewart Jones. The reaction was an early method for the oxidation of alcohols. Its use has subsided because milder, more selective reagents have been developed, e.g. Collins reagent.

<span class="mw-page-title-main">Chromyl fluoride</span> Chemical compound

Chromyl fluoride is an inorganic compound with the formula CrO2F2. It is a violet-red colored crystalline solid that melts to an orange-red liquid.

<span class="mw-page-title-main">Chromium(III) phosphate</span> Chemical compound

Chromium(III) phosphate describes inorganic compounds with the chemical formula CrPO4·(H2O)n, where n = 0, 4, or 6. All are deeply colored solids. Anhydrous CrPO4 is green. The hexahydrate CrPO4·6H2O is violet.

References

  1. 1 2 3 4 5 Lide, David R., ed. (2009). CRC Handbook of Chemistry and Physics (90th ed.). Boca Raton, Florida: CRC Press. ISBN   978-1-4200-9084-0.
  2. ↑ Seidell, Atherton; Linke, William F. (1919). Solubilities of Inorganic and Organic Compounds (2nd ed.). D. Van Nostrand Company. p.  250.
  3. ↑ "chromium(VI) oxide". chemister.ru.
  4. ↑ Pradyot, Patnaik (2003). Handbook of Inorganic Chemicals. The McGraw-Hill Companies, Inc. ISBN   0-07-049439-8.
  5. 1 2 3 Sigma-Aldrich Co., Chromium(VI) oxide. Retrieved on 2021-11-22.
  6. 1 2 3 4 "Chromium trioxide". chemicalland21.com. AroKor Holdings Inc. Retrieved 2014-06-15.
  7. 1 2 Anger, G.; Halstenberg, J.; Hochgeschwender, K.; Scherhag, C.; Korallus, U.; Knopf, H.; Schmidt, P.; Ohlinger, M. (2000). "Chromium Compounds". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a07_067. ISBN   3527306730.
  8. ↑ Mamyrbaev, Arstan Abdramanovich; Dzharkenov, Timur Agataevich; Imangazina, Zina Amangalievna; Satybaldieva, Umit Abulkhairovna (2015-04-16). "Mutagenic and carcinogenic actions of chromium and its compounds". Environmental Health and Preventive Medicine. Springer Science and Business Media LLC. 20 (3): 159–167. doi:10.1007/s12199-015-0458-2. ISSN   1342-078X. PMC   4434237 . PMID   25877777.
  9. 1 2 Cotton, F. Albert; Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred (1999), Advanced Inorganic Chemistry (6th ed.), New York: Wiley-Interscience, ISBN   0-471-19957-5
  10. ↑ Stephens, J. S.; Cruickshank, D. W. J. (1970). "The crystal structure of (CrO3)∞". Acta Crystallographica Section B. 26 (3): 222. doi:10.1107/S0567740870002182.
  11. ↑ Zhai, H. J.; Li, S.; Dixon, D. A.; Wang, L. S. (2008). "Probing the Electronic and Structural Properties of Chromium Oxide Clusters (CrO
    3    )−
    n     and (CrO3)n (n = 1–5): Photoelectron Spectroscopy and Density Functional Calculations". Journal of the American Chemical Society. 130 (15): 5167–77. doi:10.1021/ja077984d. PMID   18327905.
  12. ↑ "Chromium Trioxide (MSDS)". J. T. Baker. Archived from the original on 2015-01-12. Retrieved 2007-09-13.
  13. ↑ The environmental impact of hexavalent chromium inspired the 2000 biographical Hollywood movie Erin Brockovich .
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