Laval University From the SelectedWorks of Fathi Habashi September, 2017 Lithium 200 years Fathi Habashi Available at: https://works.bepress.com/fathi_habashi/242/ METALL-RUBMETALL-HISTORIKRISCH statesman. He was greatly honoured (Fig- Two Hundred Years Lithium ure 3). Discovery of Lithium Habashi, F. (1) When the French chemist Vauquelin ana- In 1800, Jozé Bonifacio de Andrade e Silva (1763-1838) a Brazilian scientist was lyzed spodumene in 1801 he showed a loss sent on a journey through Europe to study chemistry, mineralogy, and metallurgy. of 9.5% which he could not account for. In He was appointed as the first professor of metallurgy at the University of Coimbra 1817, the Swedish chemist Johan August in Portugal. Arfwedson (1792-1841) (Figure 4) while hile in Scandinavia he reported that he had discovered an infusible, laminated mineral from Wthe iron mine in Udö Island near Stock- holm which he called “petalite” (Figure 1) from Greek, leaf, alluding to its cleavage and another which he called “spodumene” (Figure 2) from a Greek word meaning ash colored. Fig. 4: Johan August Arfwedson (1792- 1841) working in Berzelius’ laboratory in Stock- holm analyzed petalite and spodumene and reported the presence of a new alkali Fig. 1: Petalite, LiAlSi4O10 or metal which he called “lithium” to indi- . Li2O Al2O3 8SiO2 cate that the metal was discovered in the mineral kingdom whereas the other alkali After returning to Brazil in 1819 he was metals were found in the vegetable king- appointed Minister of State and was dom. Both minerals are now known to instrumental in the independence of be lithium aluminum silicates. Another Brazil. He was a gifted poet and a great mineral also discovered on Udö Island was lepidolite, a word derived from Greek meaning scale. It has the composition K(Li,Al)(AlSi3O10)(O,OH,F)2. Arfwedson found that lithium differed from potassium in that it does not give a Fig. 2: Spodumene, LiAlSi2O6 or Fig. 3: Brazilian mineralogist José Bonifá- . Li2O Al2O3 4SiO2 cio de Andrada e Silva (1763–1838) Fig. 5: Red color in a flame due to lithium 344 9/20119/2017 | 65.71. Jahrgang | METALL METALL-HISTOMETALL-RUBRISCHRIK Fig. 6: William Thomas Brande (1788-1866) precipitate with tartaric acid, and from sodium in that its carbonate was only sparingly soluble. This last property is now used as the basis for separating lithi- um from sodium by precipitating it as the carbonate. The red color which lithium salts give to a flame (Figure 5) was first observed in 1818 by the German chemist Christian Gottolob Gmelin (1792-1860) who worked with Berzelius in Sweden before becoming professor of chemistry and pharmacy in Tübingen. Arfwedson and Gmelin tried in vain to isolate lithium metal by reduction of the oxide or by electrolysis of its salts. It was the British chemist William Thomas Fig. 8: Brines containing lithium is pumped from underground to the ponds for concent- Brande (1788-1866) (Figure 6), professor ration by evaporation in Atacama Desert of chemistry at the Royal Institution in London who used in 1813 the Greatest lithium by electrolyzing the molten chlo- Spodumene deposits Galvanic Battery to decompose the oxide. ride to study its properties. Later research The battery consisted of 20 pairs of cop- showed that lithium is widespread in the Spodumene is a hard mineral of density per and zinc plates each 1.8 m long by 0.8 mineral as well as in the animal and plant 3.15 which occurs in nature in the alpha m wide suspended from the ceiling and kingdoms. form and is not attacked by hot concen- then lowered in a tank containing about trated H2SO4. However, when it is heated 4000 L of dilute nitric and sulfuric acids. Technology at 1100°C, it is converted to the beta form, In 1855 Robert Bunsen (1811-1899) (Fig- which has a density of 2.4. When the hot ure 7) succeeded in preparing enough of Lithium is recovered from two sources: beta form is rapidly cooled, then due to lakes and underground brines, and from the volume change accompanying the spodumene deposits. phase transformation, the product can be easily crushed to a fine powder and will Lakes and underground brines react readily with hot concentrated H 2SO4. Lithium is then precipitated as carbonate Lithium-containing brines have become and recovered. an important raw material for the produc- tion of lithium chemicals. Lithium content The metal and its compounds in this source varies from 0.07 to 1.3 g/L. Production in Searles Lake just north of Lithium is an alkali metal but has prop- Los Angeles in California started in 1938. erties more similar to the alkaline earth Salar de Atacama in Antofagasta, Chile magnesium than to its group member started production in 1984. The brine is sodium. For example, lithium carbonate pumped to the surface to fill ponds lined is insoluble in water like MgCO3 unlike with nonporous membrane (Figure 8). Na2CO3. This is the basis of separating Evaporation takes place and the concen- lithium from natural brines containing trated brine is pumped to Antofagasta for alkali metals for its recovery. This proper- the precipitation of lithium carbonate. ty is known as diagonal similarity: Li simi- Production in Salar de Uyuni in south of lar to Mg, Be similar to Al, and B similar Fig. 7: Robert Bunsen (1811-1899) Bolivia did not start yet. to Si (Figure 9). METALL | 65.71. Jahrgang | 9/20119/2017 345 METALL-RUBMETALL-HISTORIKRISCH as anode and manganese dioxide as cath- ode, with a salt of lithium dissolved in an organic solvent. They are widely used in portable consumer electronic devices and in many long-life, critical devices, such as artificial pacemakers and other implant- Fig. 9: Illustrating the diagonal similarity in the Periodic Table able electronic medical devices. Lithium is a reactive metal though con- at 600 – 1000°C. Table 1 gives some data Medicine siderably less so than other alkali metals. on the metal. A freshly cut surface of lithium metal has Lithium salts have been widely used for the a silvery lustre. At room temperature in Alloys clinical treatment of depressive illnesses. dry air with a relative humidity of less Therapeutic doses of 170 – 280 mg Li per than 1%, the surface remains shiny for Aluminum-lithium alloys have been devel- day, mainly in the form of lithium carbon- several days. Lithium metal can there- oped primarily to reduce the weight of air- ate, are administered over long periods. fore be processed in dry air. However, craft and aerospace structures: density of in moist air a gray coating, consisting aluminum is 2.7 while that of lithium is 0.5. References mainly of lithium nitride, lithium oxide, The solubility limit of lithium in aluminum - F. Habashi, The Story of Metals - Volume 2, and lithium hydroxide, forms within a is 4.2%. The first aluminum-lithium alloy Métallurgie Extractive Québec 2015. Distrib- few seconds. Lithium reacts with hydro- containing 0.1% lithium was developed in uted by Laval University Bookstore, www. zone.ul.ca gen to form lithium hydride. This reac- 1924 in Germany. During the 1980s these - F. Habashi, Chemistry and Metallurgy in tion is carried out on an industrial scale alloys have been developed further by alu- the Great Empires, Métallurgie Extractive Québec, Québec City, Canada 2009. Distrib- minum producers. Alloys containing up to uted by Laval University Bookstore, www. Relative abundance 6.5x10-3 % 2.5% lithium have been produced. zone.ul.ca - M. E. Weeks, The Discovery of the Elements, Density 0.534 Journal of Chemical Education, Easton, PA Batteries 1956 Melting point 180 °C Boiling point 1342 °C Lithium batteries have lithium metal or (1) Fathi Habashi, Department of Mining, Crystalline form Body-centered cubic lithium compounds as an anode. They Metallurgical, and Materials Engi- have long life and are rechargeable. The neering, Laval University, Quebec City, Table 1: Data on lithium most common type uses metallic lithium Canada Pforzheimer Werkstofftag 2017, 28. September 2017, CongressCentrum Pforzheim Nach erfolgreichen Veranstaltungen in den vergangenen Jahren findet der Pforz- heimer Werkstofftag 2017 bereits zum sechsten Mal statt. Die eintägige Fachver- anstaltung wird organisiert vom Institut für Werkstoffe und Werkstofftechnologi- en der Hochschule Pforzheim (IWWT) sowie vom städtischen Eigenbetrieb Wirtschaft und Stadtmarketing Pforz- heim (WSP) mit seiner Cluster-Initiative HOCHFORM. Der diesjährige Werkstoff- tag setzt seinen inhaltlichen Schwerpunkt auf „Edelmetalle|Technologiemetalle – von der Tradition zur Innovation“. Darüber hinaus werden auch allgemeine Themen rund um die Werkstoffkunde, -technik und -prüfung im Rahmen der Veranstaltung aufgegriffen. Foto: Hochschule Pforzheim Informationen: www.pforzheimer-werkstofftag.de Eindruck vom letzten Werkstofftag in Pforzheim www.hs-pforzheim.de/iwwt www.hochform-pforzheim.de 346 9/20119/2017 | 65.71. Jahrgang | METALL.