23
  V  
50.941500
Vanadium

Name: Vanadium
Symbol: V
Atomic Number: 23
Atomic Weight: 50.941500
Family: Transition Metals
CAS RN: 7440-62-2
Description: A silvery grey metal
State (25 C): Solid
Oxidation states: +2, +3, +4, +5

Molar Volume: 8.55 cm3/mole
Valence Electrons: 3d34s2

Boiling Point:  3682K, 3409C, 6168F
Melting Point:
2183K, 1902C, 3470F
Electrons Energy Level: 2, 8, 11, 2
Isotopes: 25 + 1 Stable
Heat of Vaporization: 0.452 kJ/mol
Heat of Fusion: 20.9 kJ/mol
Density: 6.11 g/cm3 @ 300K
Specific Heat: 0.49 J/gK
Atomic Radius: 1.92
Ionic Radius: 0.59
Electronegativity: 1.63 (Pauling); 1.85 (Allrod Rochow)
Vapor Pressure: 3.06 Pa @ 1902C

1s2 2s2p6 3s2p6d3 4s2

History

Vanadium was originally discovered by Andres Manuel de Rio (a Spanish-born Mexican mineralogist) in Mexico City, in 1801.  He called it "brown lead" (now named vanadinite).  Through experimentation, its colors reminded him of chromium, so he named the element panchromium.  Rio sent samples of vanadium ore and a letter describing his methods to the Institute de France in Paris, France, for analysis and confirmation.  Unfortunately for Rio, his letter was lost in a shipwreck and the Institute only received his samples, which contained a brief note describing this new element, which Rio had renamed erythronium, since most of the salts turned red when heated. 

The French chemist Hippolyte Victor Collet-Descotils incorrectly declared that del Rio's new element was only impure chromium.   Del Rio thought himself to be mistaken and accepted the statement of the French chemist that was also backed by Del Rio's friend Baron Alexander von Humboldt.

In 1831, Nils Gabriel Sefstrm of Sweden rediscovered vanadium in a new oxide he found while working with some iron ores and later that same year Friedrich Wohler confirmed del Rio's earlier work.  Later, George William Fetherstonhaugh, one of the first US geologists, suggested that the element should be named "rionium" after Del Rio, but this never happened.

Metallic vanadium was isolated by  Sir Henry Enfield Roscoe an English chemist,   in 1867, who reduced vanadium (III) chloride, VCl3, with hydrogen gas, H2.  The name vanadium comes from Vanadis, a goddess in Scandinavian mythology, because the element has beautiful multicolored chemical compounds.

Characteristics

Vanadium is a soft and ductile, silver-grey metal. It has good resistance to corrosion by alkalis, sulfuric and hydrochloric acid.  It oxidizes readily at about 933oK.   Vanadium has good structural strength and a low fission neutron cross section, making it useful in nuclear applications.  Although a metal, it shares with chromium and manganese the property of having valency oxides with acid properties.

1s2
2s2 2p6
3s2 3p6 3d3
4s2

Common oxidation states of vanadium include +2, +3, +4 and +5.  A popular experiment with ammonium vanadate, NH4VO3, reducing the compound with zinc metal, can demonstrate colorimetrically all four of these vanadium oxidation states. A +1 oxidation state is rarely seen.

Occurrence

Vanadium is never found unbound in nature but it does occur in about 65 different minerals among which are patronite VS4, vanadnite, Pb5(VO4)3Cl, and carnotite, K2(UO2)2(VO4)23H2O.   Vanadium is also present in bauxite, and in carbon containing deposits such as crude oil, coal, oil shale and tar sands.  Vanadium has also been detected spectroscopically in light from the Sun and some other stars.

Much of the vanadium metal being produced is now made by calcium reduction V2O5 in a pressure vessel.  Vanadium is usually recovered as a by-product or co-product, and so world resources of the element are not really indicative of available supply.

Applications

Approximately 80% of vanadium produced is used as ferrovanadium or as a steel additive.   Other uses:

Biological

In biology, a vanadium atom is an essential component of some enzymes, particularly the vanadium nitrogenase used by some nitrogen-fixing micro-organisms.  Vanadium is essential to ascidians or sea squirts in vanadium chromogen proteins.  The concentration of vanadium in their blood is more than 100 times higher than the concentration of vanadium in the seawater around them.  Rats and chickens are also known to require vanadium in very small amounts and deficiencies result in reduced growth and impaired reproduction.

Administration of oxovanadium compounds has been shown to alleviate diabetes mellitus symptoms in certain animal models and humans.  Much like the chromium effect on sugar metabolism, the mechanism of this effect is unknown.

Supplements

Vanadium pentoxide, V2O5, is marketed in Japan as a good mineral health supplement naturally occurring in drinking water.  The source of this drinking water is mainly the slopes of Mount Fuji.  The water's vanadium pentoxide content ranges from about 60 to 130 g/liter. It is marketed as being effective against diabetes, eczema, and obesity.  There is no mention of its toxicity in the marketing of these products.

Isolation

Vanadium is available commercially and production of a sample in the laboratory is not normally required.  Commercially, routes leading to metallic vanadium as main product are not usually required as enough is produced as byproduct in other processes.

In industry, heating of vanadium ore or residues from other processes with salt, NaCl,   or sodium carbonate,  Na2CO3, at about 850C gives sodium vanadate, NaVO3.  This is dissolved in water and acidified to give a red solid which in turn is melted to form a crude form of vanadium pentoxide, V2O5.   Reduction of vanadium pentoxide with calcium gives pure vanadium. An alternative suitable for small scales is the reduction of vanadium pentachloride, VCl5, with hydrogen or magnesium.  Many other methods are also in use.

Industrially, most vanadium is used as an additive to improve steels.  Rather than proceed via pure vanadium metal it is often sufficient to react the crude of vanadium pentoxide, V2O5, with crude iron.  This produces ferrovanadium suitable for further work.

Compounds

Vanadium pentoxide, V2O5, is used as a catalyst principally in the production of sulfuric acid.  It is the source of vanadium used in the manufacture of ferrovanadium.  It can be used as a dye and color-fixer.

Vanadyl sulfate, VOSO4, also called vanadium (IV) sulfate oxide hydrate, is used as a relatively controversial dietary supplement, primarily for increasing insulin levels and body-building.  Whether it works for the latter purpose has not been proven, and there is some evidence that athletes who take it are merely experiencing a placebo effect.

Vanadium (IV) chloride, VCl4,  is a soluble form of vanadium that is commonly used in the laboratory.  Vanadium (IV) is the reduced form of Vanadium (V), and commonly occurs after anaerobic respiration by dissimilatory metal reducing bacteria.   VCl4 reacts violently with water.

Oxidation States

It is known that vanadium gets the oxidation states +2, +3, +4, +5.  To observe the colours of these states, ammonium metavanadate, NH4VO3, can be used as a starting agent.  It must be acidified beforehand so dioxovanadium (V) ion, VO2+ (yellow +5 oxidation number) is produced.  In alkaline medium, the stable form of vanadium(V) state is VO3-.

Adding zinc powder and concentrated hydrochloric acid continuously, VO2+ is reduced into blue VO2+.

It can be seen that during the reaction, the mixture is green in colour as the original yellow of the +5 state and the blue of the +4 are present.

Continuously adding Zn powder and concentrated HCl, blue VO2+ is reduced to green V3+.  V3+ is then reduced to violet V2+ by Zn powder and concentrated HCl again.

Isotopes

Naturally occurring vanadium is composed of one stable isotope 51V and one radioactive isotope 50V with a half-life of 1.51017 years.   25 artificial radioisotopes have been characterized (in the range of mass number between 40 and 65) with the most stable being 49V with a half-life of 330 days, and 48V with a half-life of 15.9735 days.  All of the remaining radioactive isotopes have half-lives shorter than an hour, the majority of them below 10 seconds. In 4 isotopes, metastable excited states were found (including 2 metastable states for 60V).

The primary decay mode before the most abundant stable isotope 51V is electron capture.  The next most common mode is beta decay.  The primary decay products before 51V are element 22 (titanium) isotopes and the primary products after are element 24 (chromium) isotopes.

atom.gif (700 bytes)

Isotope Atomic Mass Half-Life
V40 40.011  
V41 40.999  
V42 41.991 <55 ns
V43 42.981 >800 ms
V44 43.9744 90 ms
V45 44.9658 547 ms
V46 45.9602 422.37 ms
V47 46.9549 32.6 minutes
V48 47.9523 15.9735 days
V49 48.9485 330 days
V50 49.9472 1.4E 17 years
V51 50.944 Stable
V52 51.9448 3.743 minutes
V53 52.9443 1.61 minutes
V54 53.9464 49.8 seconds
V55 54.947 6.54 seconds
V56 55.95 230 ms
V57 56.952 320 ms
V58 57.957 200 ms
V59 58.959 130 ms
V60 59.965 200 ms
V61 60.967 >150 ns
V62 61.973 > 150 ns
V63 62.977 17 ms
V64 63.983 >300 ns
v65 64.988 ~10 ms

Precautions

80px-Flammable.jpg (2186 bytes) Powdered metallic vanadium is a fire hazard, and unless known otherwise, all vanadium compounds should be considered highly toxic.   Generally, the higher the oxidation state of vanadium, the more toxic the compound is. he most dangerous compound is vanadium pentoxide.

The Occupational Safety and Health Administration (OSHA) has set an exposure limit of 0.05 mg/m3 for vanadium pentoxide dust and 0.1 mg/m3 for vanadium pentoxide fumes in workplace air for an 8-hour workday, 40-hour work week.

40px-Skull_and_crossbones.svg.jpg (1420 bytes) The National Institute for Occupational Safety and Health (NIOSH) has recommended that 35 mg/m3 of vanadium be considered immediately dangerous to life and health.  This is the exposure level of a chemical that is likely to cause permanent health problems or death.

There is little evidence that vanadium or vanadium compounds are reproductive toxins or teratogens.  There is also no evidence that any vanadium compound is carcinogenic; however, very few adequate studies are available for evaluation. Vanadium has not been classified as to carcinogenicity by the U.S. EPA (1991a).

40px-Skull_and_crossbones.svg.jpg (1420 bytes) The toxicity of vanadium depends on its physico-chemical state; particularly on its valence state and solubility.  Pentavalent VOSO4 has been reported to be more than 5 times as toxic as trivalent V2O3 (Roschin, 1967). 

Vanadium compounds are poorly absorbed through the gastrointestinal system.   Inhalation exposures to vanadium and vanadium compounds result primarily in adverse effects to the respiratory system (Sax, 1984; ATSDR, 1990). Quantitative data are, however, insufficient to derive a subchronic or chronic inhalation.


atom.gif (700 bytes)

Vanadium Data
 

Atomic Structure

  • Atomic Radius: 1.92
  • Atomic Volume: 8.78cm3/mol
  • Covalent Radius: 1.22
  • Cross Section (Thermal Neutron Capture) Barn: 5.08
  • Crystal Structure: Cubic body centered
  • Electron Configuration:
    1s2 2s2p6 3s2p6d3 4s2
  • Electrons per Energy Level: 2, 8, 11, 2
  • Ionic Radius: 0.59
  • Filling Orbital: 3d3
  • Number of Electrons (with no charge): 23
  • Number of Neutrons (most common/stable nuclide): 28
  • Number of Protons: 23
  • Oxidation States: 5, 3
  • Valence Electrons: 3d3 4s2

Chemical Properties

  • Electrochemical Equivalent: 0.38013 g/amp-hr
  • Electron Work Function: 4.3eV
  • Electronegativity: 1.63 (Pauling); 1.85 (Allrod Rochow)
  • Heat of Fusion: 20.9 kJ/mol
  • Incompatibilities:
    Strong oxidizers, ammonium nitrate
  • Ionization Potential
    • First: 6.74
    • Second: 14.65
    • Third: 29.31
  • Valence Electron Potential (-eV): 120

Physical Properties

  • Atomic Mass Average: 50.9415
  • Boiling Point: 3682K, 3409C, 6168F
  • Coefficient of Lineal Thermal Expansion/K-1: 8.3E-6
  • Conductivity
    Electrical: 0.0489 106/cm
    Thermal: 0.307 W/cmK
  • Density: 6.11 g/cm3 @ 300K
  • Description:
    Silvery-white metal.
  • Elastic Modulus:
    • Bulk: 158/GPa
    • Rigidity: 46.7/GPa
    • Youngs: 127.6/GPa
  • Enthalpy of Atomization: 514.6 kJ/mole @ 25C
  • Enthalpy of Fusion: 17.57 kJ/mole
  • Enthalpy of Vaporization: 458.6 kJ/mole
  • Flammablity Class: Non-combustible solid (except as dust)
  • Freezing Point: see melting point
  • Hardness Scale
    • Brinell: 628 MN m-2
    • Mohs: 6.7
    • Vickers: 628 MN m-2
  • Heat of Vaporization: 0.452 kJ/mol
  • Melting Point: 2183K, 1902C, 3470F
  • Molar Volume: 8.55 cm3/mole
  • Optical Reflectivity: 61%
  • Physical State (at 20C & 1atm): Solid
  • Specific Heat: 0.49 J/gK
  • Vapor Pressure: 3.06 Pa @ 1902C

Regulatory / Health

  • CAS Number
    • 7440-62-2
  • OSHA Permissible Exposure Limit (PEL)
    • No limits set by OSHA
  • OSHA PEL Vacated 1989
    • No limits set by OSHA
  • NIOSH Recommended Exposure Limit (REL)
    • No limits set by NIOSH
  • Routes of Exposure: Inhalation; Ingestion; Skin and/or eye contact
  • Target Organs: Skin, respiratory system
  • Levels In Humans:
    Note: this data represents naturally occuring levels of elements in the typical human, it DOES NOT represent recommended daily allowances.
    • Blood/mg dm-3: <0.0002
    • Bone/p.p.m: 0.0035
    • Liver/p.p.m: 0.006
    • Muscle/p.p.m: 0.02
    • Daily Dietary Intake: 0.04 mg
    • Total Mass In Avg. 70kg human: 0.11 mg
  • Discovery Year: 1801
  • Name Origin:
    From Vanadis a Scandinavian goddess.
  • Abundance:
    • Earth's Crust/p.p.m.: 160
    • Seawater/p.p.m.:
      • Atlantic Suface: 0.0011
      • Atlantic Deep: N/A
      • Pacific Surface: 0.0016
      • Pacific Deep: 0.0018
    • Atmosphere/p.p.m.: N/A
    • Sun (Relative to H=1E12): 10500
  • Sources:
    Found in the minerals patronite (VS4), vanadinite [Pb5(VO4)3Cl], and carnotite [K2(UO2)2(VO4)2.3H2O]. Vanadium is usually produced as a by-product of refining other ores and from Venezuelan oils. Annual world wide production is around 7,000 tons.
  • Uses:
    It is mixed with other metals to make very strong and durable alloys which are used in construction materials, tools, springs and jet engines. Vanadium pentoxide (V2O5) is used as a catalyst, dye and color-fixer.
  • Additional Notes:
    Many sources credit Nils Sefstrm with discovering vanadium in 1831, however, this is more of a rediscovery as it had already been discovered in A.M. del Rio in 1801.

Ionization Energy (eV): 6.746 eV
Estimated Crustal Abundance: 1.20102 milligrams per kilogram
Estimated Oceanic Abundance:
2.510-3 milligrams per liter

Transition Metals
Group 3
(IIIB)
4
(IVB)
5
(VB)
6
(VIB)
7
(VIIB)
8
(VIIIB)
9
(VIIIB)
10 (VIIIB) 11
(IB)
12
(IIB)
Period 4 21
Sc
44.95
22
Ti
47.86
23
V
50.94
24
Cr
51.99
25
Mn
54.93
26
Fe
55.84
27
Co
58.93
28
Ni
58.69
29
Cu
63.54
30
Zn
65.39
Period 5 39
Y
88.90
40
Zr
91.22
41
Nb
92.90
42
Mo
95.94
43
Tc
98.00
44
Ru
101.0
45
Rh
102.9
46
Pd
106.4
47
Ag
107.8
48
Cd
112.4
Period 6 57
La
138.9
72
Hf
178.4
73
Ta
180.9
74
W
183.8
75
Re
186.2
76
Os
190.2
77
Ir
192.2
78
Pt
195.0
79
Au
196.9
80
Hg
200.5
Period 7 89
Ac
227.0
104
Rf
261.0
105
Db
262.0
106
Sg
266.0
107
Bh
264.0
108
Hs
269.0
109
Mt
268.0
110
Ds
269.0
111
Rg
272.0
112
Uub
277.0