Vanadium, discovery

Earlier, in 1801 in Mexico, Andres Manuel del Rio, a chemist and mineralogist, discovered an unusual substance he called erythronium, but he was told it was similar to chromium. Only later was it found to be vanadium. Some early references credit Del Rio with vanadiums discovery, but the most recent references list Sefstrom as the discoverer. 

Our knowledge of the different twists in the final phase of the discovery of vanadium is founded on the correspondence between Berzelius and Wohler just before and after the year 1830. The correspondence confirms that Sefstrom s vanadium discovery was made public before Wohler could confirm that Del Rio s erythronium was a new element and identical with Sefstrom s vanadium. 

Vanadium was first discovered in 1801 by del Rio while he was examining a lead ore obtained from Zimapan, Mexico. The ore contained a new element and, because of the red color imparted to its salts on heating, it was named erythronium (redness). The identification of the element vanadium did not occur until 1830 when it was isolated from cast iron processed from an ore from mines near Taberg, Sweden. It was given the name vanadium after Vanadis, the Norse goddess of beauty. Shordy after this discovery, vanadium was shown to be identical to the erythronium that del Rio had found several years eadier. 

A number of nitrogen-fixing bacteria contain vanadium and it has been shown that in one of these, Azotobacter, there are three distinct nitrogenase systems based in turn on Mo, V and Fe, each of which has an underlying functional and structural similarity.This discovery has prompted a search for models and the brown compound [Na(thf)]+[V(N2)2(dppe)2] (dppe = Pli2PCH2CH2PPh2) has recently been prepared by reduction of VCI3 by sodium naphthalenide... 

Just a few years after the discovery of the deposition and electroactivity of Prussian blue, other metal hexacyanoferrates were deposited on various electrode surfaces. However, except for ruthenium and osmium, the electroplating of the metal or its anodizing was required for the deposition of nickel [14], copper [15,16], and silver [9] hexacyanoferrates. Later studies have shown the possibilities of the synthesis of nickel, cobalt, indium hexacyanoferrates similar to the deposition of Prussian blue [17-19], as well as palladium [20-22], zinc [23, 24], lanthanum [25-27], vanadium [28], silver [29], and thallium [30] hexacyanoferrates. 

The lower oxidation states are stabilized by soft ligands e.g. CO (Prob. 3). The aquated vanadium ions represent an interesting series of oxidation states. They are all stable with respect to disproportionation and labile towards substitution. They undergo a number of redox reactions with one another, all of which have been studied kinetically. Many of the reactions are [H ]-dependent. There has been recent interest in the biological aspects of vanadium since the discovery that vanadate can mimic phosphate and act as a potent inhibitor (Prob. 4). 

Two unrelated discoveries of vanadium seem to have occurred. When he was experimenting with iron in 1830, Nils Gabriel Sefstrom (1787—1845), a Swedish chemist and mineralogist, identified a small amount of a new metal. Because vanadium compounds have beautiful colors, he named this new metal after Vanadis, the mythological goddess of youth and beauty in his native country, Scandinavia. 

Sometime later in 1869, vanadium metal was isolated from its ores by Henry Enfield Roscoe (1833—1915), but Sefstrom had already received credit for the discovery of the element vanadium. 

The final step in the discovery of vanadium was accomplished by the English chemist, Sir Henry Enfield Roscoe, who was bom in London on January 7, 1833. When he was nine years old the family moved to... 

The most outstanding achievement of del Rio s long, useful life was his discovery in 1801 of the metal now known as vanadium. He found that the brown lead mineral, Plomo pardo de Zimapan (8), from the... 

The details of N. G. Sefstrom s discovery of vanadium in soft iron from the Taberg Mine in Smaland, Sweden, and of F. Wohler s proof of the identity of erythronium and vanadium have already been related (14, 15, 16). Dr. Enrique Moles emphasized the fact that del Rio s own excessive modesty and scientific caution led him to renounce the discovery of the new element before the analysis of Collet-Descotils had been published. 

Sjoberg, S. G., Nils Gabriel Sefstrom and the discovery of vanadium, J. 

Since the discovery of hexacarbonylvanadium(O) and hexacarbonylvanadate( 1-) by Calderazzo and co-workers in 1959 and 1960, these substances have been key precursors to a variety of vanadium compounds, including inorganic noncarbonyl species, organovanadium complexes," and other vanadium carbonyls. Neutral V(CO)6 is of special interest in that it is the only isolable 17-electron homoleptic metal carbonyl and exhibits fascinating chemical properties that are often reminiscent of iodine and classic pseudohalogens. ... 

Since the discovery by Cantley et al. that vanadate is a powerful and allosteric inhibitor of Na+,K+-ATPase,921 vanadium began to interest biochemists and Chasteen has reviewed work published up to 1983.471 Particularly interesting new studies involve vanadium peroxidases946 and nitrogenases.947... 

Since discovery of MCM-41 materials [1,2] many researchers have been concentrated on the improvement of their quality and properties by incorporating heteroatoms such as titanium [3-5], boron [6,7], vanadium [8], gallium [9], and recently lanthanides (mainly La and Ce) [10-13]. Incorporation of these elements into the MCM-41 structure influences its stability as well as adsorption and catalytic properties [13]. The presence of silanol groups on the surface of these mesoporous materials allows for bonding of organic and inorganic ligands [14-16]. 

The industrial application of vanadium received its main impetus, however, when the metal entered the domain of metallurgy. In 1893 Moissan applied his electric furnace to the making of alloys of vanadium, and produced ferrovanadium in large quantity. The mechanical properties of vanadium steels were noted by Helouis in 1896,2 but were first thoroughly investigated at Sheffield, England, by Professor Arnold in 1900 (see p. 26), whose work was followed by that of Sankey and Smith in 1904. The discovery of the vast Peruvian deposits in 1905 was followed by the successful preparation from them of a ferrovanadium alloy which could readily be employed in the manufacture of vanadium steels. This process now absorbs nearly all the world s production of vanadium. 

They are isomorphous also with the calcium compounds Ca3(V04)2. CaCl2 and Ca3(P04)2.CaCl2.5 The discovery of isomorphism among these double salts led Roscoe to transfer vanadium from the chromium family, in which it had been previously placed, to Group V. (see p. 2 1). 

This volume deals with the chemistry of vanadium, niobium, and tantalum. These elements are all of comparatively recent discovery, none of them being known before the nineteenth century. 

The first suggestion of a possible biochemical function for vanadium came from the discovery that vanadocytes, the green blood cells of tunicates (sea squirts), contain 1.0 M V(III) and 1.5-2 M H2S04. 613 It was proposed that a V-containing protein is an oxygen carrier. However, the V3+ appears not to be associated with proteins612 and it does not carry 02. 

Much of current interest in vanadium stems from the discovery that vanadate (HV042 at pH 7) is a powerful inhibitor of ATPases such as the sodium pump protein (Na+ + K+)ATPase (Chapter 8), of phosphatases,623 and of kinases.624 This can be readily understood from comparison of the structure of phosphate and vanadate ions. 

VANADINITE. The mineral vanadimte corresponds to the formula Pb VO Cl, being composed of lead chloride and lead vanadate in the proportion of 90.2% of the former and 9.8% of the latter. It crystallizes in the hexagonal system, is usually prismatic, but the ciystals are often skeletal or cavernous it may be found in crusts. Its fracture is uneven brittle hardness. 2.75-3 specific gravity. 6.86 fresh fractures show a resinous luster color, yellow, yellowish-brown, reddish-brown, and red streak, white to yellowish translucent to opaque. Vanadinite, not a common mineral, occurs as an alteration product in lead deposits. It is found in the Ural Mountains, Austria, Spain, Scotland, Morocco, the Transvaal, Argentina, and Mexico, In the United States it occurs in Arizona, New Mexico, and South Dakota, It is used as an ore of vanadium and to some extent of lead as well. It is interesting to note that this mineral was first described as a chromate upon its discovery in Mexico in 1801, It was not until the discovery of the element vanadium in 1830 that the true nature of this compound was known. 

The striking advance since 1973 has been the synthesis of homoleptic isocyanides for vanadium and almost all of the post-group-VIA metals up to group IB (see Table I), and this has been helped in some respects by synthetic rationale. For example, the discovery of the simple reductive or nonreduc-tive cleavage of multiple metal-metal bonds in suitable dinuclear complexes of molybdenum and tungsten has provided a high yield route to W(CNPh)6 and [M(CNR)7]2+ (M = Mo, W) and related complexes (5-14). During these studies the series [M(CNR)7]2+ was completed with the isola-... 

Previously proposed mechanisms of the biosynthesis of certain chlorinated compounds have invoked electrophilic bromination of alkenes followed by passive chloride attack [62], Although this mechanism could explain the origin of adjacent brominated and chlorinated carbons, it does not readily account for compounds containing chlorine only. Thus, with the discovery of chloroperoxidase activity of the vanadium enzyme, the origin of specific chlorinated marine natural products can now be addressed. 

Vanadium(II) homogeneous systems reduce dinitrogen to ammonia very cleanly and efficiently, and there is no dispute about them. The original discovery was that vanadium(II) plus polyphenols in homogeneous alkaline solution in a very restricted pH range reduces dinitrogen to ammonia according to Eq. (79) (198). 

---