Chemistry:Vanadium(V) oxide

Short description: Precursor to vanadium alloys and industrial catalyst

Vanadium(V) oxide

Names
IUPAC name Divanadium pentaoxide
Other names Vanadium pentoxide Vanadic anhydride Divanadium pentoxide
Identifiers
CAS Number	1314-62-1 Y
3D model (JSmol)	Interactive image
ChEBI	CHEBI:30045 Y
ChemSpider	14130 Y
EC Number	215-239-8
KEGG	C19308 N
PubChem CID	14814
RTECS number	YW2450000
UNII	BVG363OH7A Y
UN number	2862
InChI InChI=1S/5O.2V Y Key: GNTDGMZSJNCJKK-UHFFFAOYSA-N Y InChI=1/5O.2V/rO5V2/c1-6(2)5-7(3)4 Key: GNTDGMZSJNCJKK-HHIHJEONAP
SMILES O=[V](=O)O[V](=O)=O
Properties
Chemical formula	V2O5
Molar mass	181.8800 g/mol
Appearance	Yellow solid
Density	3.35 g/cm3
Melting point	681 °C (1,258 °F; 954 K)
Boiling point	1,750 °C (3,180 °F; 2,020 K) (decomposes)
Solubility in water	0.7 g/L (20 °C)
Magnetic susceptibility (χ)	+128.0·10−6 cm3/mol
Structure
Crystal structure	Orthorhombic
Space group	Pmmn, No. 59
Lattice constant	a = 1151 pm, b = 355.9 pm, c = 437.1 pm
Coordination geometry	Distorted trigonal bipyramidal (V)
Thermochemistry
Heat capacity (C)	127.7 J/(mol·K)
Std molar entropy (So298)	131.0 J/(mol·K)
Std enthalpy of formation (ΔfH⦵298)	-1550.6 kJ/mol
Gibbs free energy (ΔfG˚)	-1419.5 kJ/mol
Hazards
Safety data sheet	ICSC 0596
GHS pictograms
GHS Signal word	DANGER
GHS hazard statements	H341, H361, H372, H332, H302, H335, H411
NFPA 704 (fire diamond)	0 4 0
Flash point	Non-flammable
Lethal dose or concentration (LD, LC):
LD50 (median dose)	10 mg/kg (rat, oral) 23 mg/kg (mouse, oral)
LCLo (lowest published)	500 mg/m3 (cat, 23 min) 70 mg/m3 (rat, 2 hr)
NIOSH (US health exposure limits):
PEL (Permissible)	C 0.5 mg V2O5/m3 (resp) (solid) C 0.1 mg V2O5/m3 (fume)
Related compounds
Other anions	Vanadium oxytrichloride
Other cations	Niobium(V) oxide Tantalum(V) oxide
Related vanadium oxides	Vanadium(II) oxide Vanadium(III) oxide Vanadium(IV) oxide
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

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Vanadium(V) oxide (vanadia) is the inorganic compound with the formula V₂O₅. Commonly known as vanadium pentoxide, it is a brown/yellow solid, although when freshly precipitated from aqueous solution, its colour is deep orange. Because of its high oxidation state, it is both an amphoteric oxide and an oxidizing agent. From the industrial perspective, it is the most important compound of vanadium, being the principal precursor to alloys of vanadium and is a widely used industrial catalyst.

The mineral form of this compound, shcherbinaite, is extremely rare, almost always found among fumaroles. A mineral trihydrate, V₂O₅·3H₂O, is also known under the name of navajoite.

Chemical properties

Reduction to lower oxides

Upon heating a mixture of vanadium(V) oxide and vanadium(III) oxide, comproportionation occurs to give vanadium(IV) oxide, as a deep-blue solid:

V₂O₅ + V₂O₃ → 4 VO₂

The reduction can also be effected by oxalic acid, carbon monoxide, and sulfur dioxide. Further reduction using hydrogen or excess CO can lead to complex mixtures of oxides such as V₄O₇ and V₅O₉ before black V₂O₃ is reached.

Acid-base reactions

V₂O₅ is an amphoteric oxide. Unlike most transition metal oxides, it dissolves slightly in water to give a pale yellow, acidic solution. Thus V₂O₅ reacts with strong non-reducing acids to form solutions containing the pale yellow salts containing dioxovanadium(V) centers:

V₂O₅ + 2 HNO₃ → 2 VO₂(NO₃) + H₂O

It also reacts with strong alkali to form polyoxovanadates, which have a complex structure that depends on pH. If excess aqueous sodium hydroxide is used, the product is a colourless salt, sodium orthovanadate, Na₃VO₄. If acid is slowly added to a solution of Na₃VO₄, the colour gradually deepens through orange to red before brown hydrated V₂O₅ precipitates around pH 2. These solutions contain mainly the ions HVO₄²⁻ and V₂O₇⁴⁻ between pH 9 and pH 13, but below pH 9 more exotic species such as V₄O₁₂⁴⁻ and HV₁₀O₂₈⁵⁻ (decavanadate) predominate.

Upon treatment with thionyl chloride, it converts to the volatile liquid vanadium oxychloride, VOCl₃:

V₂O₅ + 3 SOCl₂ → 2 VOCl₃ + 3 SO₂

Other redox reactions

Hydrochloric acid and hydrobromic acid are oxidised to the corresponding halogen, e.g.,

V₂O₅ + 6HCl + 7H₂O → 2[VO(H₂O)₅]²⁺ + 4Cl⁻ + Cl₂

Vanadates or vanadyl compounds in acid solution are reduced by zinc amalgam through the colourful pathway:

VO₂⁺yellow → VO²⁺blue → V³⁺green → V²⁺purple

The ions are all hydrated to varying degrees.

Preparation

The orange, partly hydrated form of V₂O₅

Precipitate of "red cake", which is hydrous V₂O₅

Technical grade V₂O₅ is produced as a black powder used for the production of vanadium metal and ferrovanadium. A vanadium ore or vanadium-rich residue is treated with sodium carbonate and an ammonium salt to produce sodium metavanadate, NaVO₃. This material is then acidified to pH 2–3 using H₂SO₄ to yield a precipitate of "red cake" (see above). The red cake is then melted at 690 °C to produce the crude V₂O₅.

Vanadium(V) oxide is produced when vanadium metal is heated with excess oxygen, but this product is contaminated with other, lower oxides. A more satisfactory laboratory preparation involves the decomposition of ammonium metavanadate at 500–550 °C:

2 NH₄VO₃ → V₂O₅ + 2 NH₃ + H₂O

Uses

Ferrovanadium production

In terms of quantity, the dominant use for vanadium(V) oxide is in the production of ferrovanadium (see above). The oxide is heated with scrap iron and ferrosilicon, with lime added to form a calcium silicate slag. Aluminium may also be used, producing the iron-vanadium alloy along with alumina as a byproduct.

Sulfuric acid production

Another important use of vanadium(V) oxide is in the manufacture of sulfuric acid, an important industrial chemical with an annual worldwide production of 165 million tonnes in 2001, with an approximate value of US$8 billion. Vanadium(V) oxide serves the crucial purpose of catalysing the mildly exothermic oxidation of sulfur dioxide to sulfur trioxide by air in the contact process:

2 SO₂ + O₂ ⇌ 2 SO₃

The discovery of this simple reaction, for which V₂O₅ is the most effective catalyst, allowed sulfuric acid to become the cheap commodity chemical it is today. The reaction is performed between 400 and 620 °C; below 400 °C the V₂O₅ is inactive as a catalyst, and above 620 °C it begins to break down. Since it is known that V₂O₅ can be reduced to VO₂ by SO₂, one likely catalytic cycle is as follows:

SO₂ + V₂O₅ → SO₃ + 2VO₂

followed by

2VO₂ +½O₂ → V₂O₅

It is also used as catalyst in the selective catalytic reduction (SCR) of NO_x emissions in some power plants and diesel engines. Due to its effectiveness in converting sulfur dioxide into sulfur trioxide, and thereby sulfuric acid, special care must be taken with the operating temperatures and placement of a power plant's SCR unit when firing sulfur-containing fuels.

Other oxidations

Proposed early steps in the vanadium-catalyzed oxidation of naphthalene to phthalic anhydride, with V₂O₅ represented as a molecule vs its true extended structure

Maleic anhydride is produced by the V₂O₅-catalysed oxidation of butane with air:

C₄H₁₀ + 4 O₂ → C₂H₂(CO)₂O + 8 H₂O

Maleic anhydride is used for the production of polyester resins and alkyd resins.

Phthalic anhydride is produced similarly by V₂O₅-catalysed oxidation of ortho-xylene or naphthalene at 350–400 °C. The equation for the vanadium oxide-catalysed oxidation of o-xylene to phthalic anhydride:

C₆H₄(CH₃)₂ + 3 O₂ → C₆H₄(CO)₂O + 3 H₂O

The equation for the vanadium oxide-catalysed oxidation of naphthalene to phthalic anhydride:

C₁₀H₈ + 4½ O₂ → C₆H₄(CO)₂O + 2CO₂ + 2H₂O

Phthalic anhydride is a precursor to plasticisers, used for conferring pliability to polymers.

A variety of other industrial compounds are produced similarly, including adipic acid, acrylic acid, oxalic acid, and anthraquinone.

Other applications

Due to its high coefficient of thermal resistance, vanadium(V) oxide finds use as a detector material in bolometers and microbolometer arrays for thermal imaging. It also finds application as an ethanol sensor in ppm levels (up to 0.1 ppm).

Vanadium redox batteries are a type of flow battery used for energy storage, including large power facilities such as wind farms. Vanadium oxide is also used as a cathode in lithium ion batteries.

Biological activity

Vanadium(V) oxide exhibits very modest acute toxicity to humans, with an LD50 of about 470 mg/kg. The greater hazard is with inhalation of the dust, where the LD50 ranges from 4–11 mg/kg for a 14-day exposure. Vanadate (VO3−4), formed by hydrolysis of V₂O₅ at high pH, appears to inhibit enzymes that process phosphate (PO₄³⁻). However the mode of action remains elusive.

Cited sources

• Brauer, G. (1963). "Vanadium, Niobium, Tantalum". in Brauer, G.. Handbook of Preparative Inorganic Chemistry, 2nd Ed.. NY: Academic Press. 
• Haynes, William M., ed (2016). CRC Handbook of Chemistry and Physics (97th ed.). CRC Press. ISBN 9781498754293. 

Further reading

• "Vanadium Pentoxide", Cobalt in Hard Metals and Cobalt Sulfate, Gallium Arsenide, Indium Phosphide and Vanadium Pentoxide, IARC Monographs on the Evaluation of Carcinogenic Risks to Humans 86, Lyon, France: International Agency for Research on Cancer, 2006, pp. 227–92, ISBN 92-832-1286-X, http://monographs.iarc.fr/ENG/Monographs/vol86/mono86-10.pdf .
• Vaidhyanathan, B.; Balaji, K.; Rao, K. J. (1998), "Microwave-Assisted Solid-State Synthesis of Oxide Ion Conducting Stabilized Bismuth Vanadate Phases", Chem. Mater. 10 (11): 3400–4, doi:10.1021/cm980092f .

External links

• International Chemical Safety Card 0596
• NIOSH Pocket Guide to Chemical Hazards. "#0653". National Institute for Occupational Safety and Health (NIOSH). https://www.cdc.gov/niosh/npg/npgd0653.html. 
• NIOSH Pocket Guide to Chemical Hazards. "#0654". National Institute for Occupational Safety and Health (NIOSH). https://www.cdc.gov/niosh/npg/npgd0654.html. 
• Vanadium Pentoxide and other Inorganic Vanadium Compounds (Concise International Chemical Assessment Document 29)
• IPCS Environmental Health Criteria 81: Vanadium
• IPCS Health and Safety Guide 042: Vanadium and some vanadium salts