7.1 A crystal on paper

In 1801 Charles Hatchett found an unknown metal in a mineral from North America and called it columbium [III. An analysis 1802 rec]. In 1802 Anders Ekeberg named another metal tantalum, after Tantalus of Greek myth, who stood in water he could never drink; the oxide would not dissolve even in excess acid [Ekeberg 1802 P; Rose 1844 rec]. In 1809 William Hyde Wollaston argued the two were the same element [XV. On the 1809 rec], and chemists accepted that for 35 years.

In 1844 Heinrich Rose in Berlin showed that tantalite from Bavaria held a second metal. He called it niobium, after Niobe, daughter of Tantalus, “to indicate the similarity” with tantalum [Rose 1844 rec]. In 1846 he named a third, pelopium, after Niobe's brother Pelops [Rose 1846 rec]; it was niobium again. In 1818 Berzelius had already named lithium from the Greek for stone, because his student Arfwedson found it in a mineral [Arfwedson 1818 rec; Berzelius 1818 rec]. So LiNbO₃ is, by name, stone and Niobe; its sibling LiTaO₃ is stone and Tantalus.

The earliest report of the compound found is a 1928 Oslo doctoral thesis by W. H. Zachariasen, a survey of oxide crystal structures [Zachariasen 1928 P]. In 1949 Bernd Matthias and Joseph Remeika at Bell Labs reported that single crystals of LiNbO₃ and LiTaO₃ are ferroelectric: each carries a built-in electric polarization that an applied field can reverse [Matthias & Remeika 1949 rec]. In 1958 Reisman and Holtzberg mapped how lithium oxide and niobium oxide melt together [Reisman & Holtzberg 1958 rec].

Tantalus
  +-- Niobe ------ Nb   niobium, Rose 1844
  |                  =  Columbium   Hatchett 1801
  +-- Pelops ----- pelopium   Rose 1846 (= Nb)
  +-- Ta   tantalum, Ekeberg 1802
lithos ---- Li   lithium, Arfwedson 1818

Li + Nb ---- LiNbO3    stone and Niobe
Li + Ta ---- LiTaO3    stone and Tantalus

The naming sentence. Rose 1844, Ann. Phys. 139, pp. 335-336: “Ich nenne dasselbe Niobium und sein Oxyd Niobsaure, von Niobe, der Tochter des Tantalus, um durch den Namen die Aehnlichkeit ... anzudeuten” [Rose 1844 rec]. The paper was read to the Berlin Academy on 1844-10-31 [Rose 1844 rec]. Pelopium: Rose 1846, Ann. Phys. 145, p. 119, “von Pelops, dem Sohne des Tantalus, und dem Bruder der Niobe”; read 1846-07-16 [Rose 1846 rec; Rose 1846 rec].

Untangling. Rose later recognized that his “pelopic” and “niobic” acids held the same metal; Marignac (1866) identified the white chloride as NbOCl₃ and traced Rose's errors to the constant association of Nb with Ta [Marignac 1866 rec]. The name niobium was chosen internationally in 1949 and accepted by IUPAC in 1950 [Rayner-Canham & Zheng 2008 S; van der Krogt 2026 S].

Lithium. Arfwedson's paper (Afhandlingar 6, Stockholm 1818) states that Berzelius proposed “Lithion” from the Greek for stone because the alkali was first found in the mineral kingdom; the petalite came from the Uto iron mine [Arfwedson 1818 rec]. Berzelius announced it in a letter dated 1818-02-09 [Berzelius 1818 rec]. The discovery is commonly dated 1817 [Weeks 1932 P].

Ferroelectric, not ilmenite. Matthias and Remeika titled their letter “Ferroelectricity in the ilmenite structure” and wrote that Zachariasen had described LiNbO₃ (as “LiCbO₃”) “as belonging to the ilmenite structure, which is centro-symmetric” [Matthias & Remeika 1949 rec]. A centrosymmetric crystal cannot be ferroelectric, so the observation itself flagged the structural label. The 1966 Bell Labs X-ray and neutron studies fixed the structure as R3c [Abrahams et al. 1966a rec; Abrahams et al. 1966b rec]; the standard reading is that LN shares ilmenite's oxygen framework but orders its cations differently along c [Abrahams et al. 1966a P]. They also report that ceramics “show hardly any effect”, which is why single crystals mattered from the start [Matthias & Remeika 1949 rec].

Composition. Reisman and Holtzberg mapped the Li₂O-Nb₂O₅ system in 1958 [Reisman & Holtzberg 1958 rec]. Lerner, Legras and Dumas showed in 1968 that commercial crystals are Li-deficient [Lerner et al. 1968 rec]. Carruthers et al. located the congruent composition at 48.6 mol% Li₂O by ⁹³Nb NMR and Curie-temperature shifts, with a room-temperature solid solution of 48-50 mol% Li₂O [Carruthers et al. 1971 rec]. A melt at the congruent point freezes to a crystal of the same composition, so a boule is uniform end to end; that crystal is lithium-poor.

Czochralski's method. “Ein neues Verfahren zur Messung der Kristallisationsgeschwindigkeit der Metalle” measured the maximum speed at which a thin crystal thread can be drawn continuously from its melt, held in a charcoal crucible [Czochralski 1918 rec]. Received 1916-08-19, issued 1917-04-24 in volume 92, which is dated 1918.

Niobium is 1844; secondary sources that give 1846 merge the niobium and pelopium papers (English Wikipedia text cites the 1844 paper but writes 1846) [Rose 1844 rec; Rose 1846 rec].

References

1. Philosophical Transactions of the Royal Society of London 92 49-66 (1802). III. An analysis of a mineral substance from North America, containing a metal hitherto unknown. Issued 1802-12-31. doi:10.1098/rstl.1802.0005
2. Anders Gustaf Ekeberg, Kongl. Vetenskaps Academiens Nya Handlingar 68 (1802). Paper naming tantalum (as cited). Issued 1802
3. Heinrich Rose, Annalen der Physik 139 317-341 (1844). Ueber die Zusammensetzung der Tantalite und ein im Tantalite von Baiern enthaltenes neues Metall. Issued 1844-01. doi:10.1002/andp.18441391006
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7. Jons Jacob Berzelius, Annales de Chimie et de Physique 7 199-201 (1818). Letter to C. L. Berthollet announcing a new alkali (dated 1818-02-09). Issued 1818. archive.org/details/s3id13207740
8. W. H. Zachariasen, Skrifter utgitt av det Norske Videnskaps-Akademi i Oslo, I. Mat.-Naturv. Klasse 1928, No. 4 165 pp. (1928). Untersuchungen uber die Kristallstruktur von Sesquioxyden und Verbindungen ABO3. Issued 1928
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10. Reisman & Holtzberg, Journal of the American Chemical Society 80 6503-6507 (1958). Heterogeneous Equilibria in the Systems Li2O-, Ag2O-Nb2O5 and Oxide-Models. Issued 1958-12. doi:10.1021/ja01557a010
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19. Lerner et al., Journal of Crystal Growth 3-4 231-235 (1968). Stoechiométrie des monocristaux de métaniobate de lithium. Issued 1968-01. doi:10.1016/0022-0248(68)90139-5
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