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Trends in Structure and Thermodynamic Properties of Normal Rare Earth Carbonates and Rare Earth Hydroxycarbonates

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Trends in Structure and Thermodynamic Properties of Normal Rare Earth Carbonates and Rare Earth Hydroxycarbonates minerals Review Trends in Structure and Thermodynamic Properties of Normal Rare Earth Carbonates and Rare Earth Hydroxycarbonates Paul Kim 1 ID , Andre Anderko 2 ID , Alexandra Navrotsky 3 and Richard E. Riman 1,* ID 1 Department of Materials Science & Engineering, Rutgers—The State University of New Jersey, 607 Taylor Road, Piscataway, NJ 08854, USA; [email protected] 2 OLI Systems, Inc., 240 Cedar Knolls Road, Suite 301, Cedar Knolls, NJ 07927, USA; [email protected] 3 Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California Davis, Davis, CA 95616, USA; [email protected] * Correspondence: [email protected]; Tel.: +1-848-445-4946 Received: 28 January 2018; Accepted: 23 February 2018; Published: 7 March 2018 Abstract: A general overview of the trends in structural and thermodynamic properties that have been identified within the hydrated normal rare earth carbonates and the rare earth hydroxycarbonates is presented. Based upon available literature, we demonstrate the trends in crystallographic unit cell parameters, thermal stability, aqueous solubility, and thermochemical properties. These trends can be attributed to both the unique chemistry and strong similarity of the rare earth elements. There are also inconsistent trends that signal research needs to better understand the structure–energy relationships of the rare earth carbonates. Keywords: thermodynamic properties; rare-earth carbonates; property correlations; normal carbonates; hydroxycarbonates 1. Introduction The rare earth elements have made their way into many aspects of modern life. From the gasoline in automobiles, the ubiquitous mobile phones, speakers, lights, to energy production, the rare earth elements are indispensable to current standards of living and technology. Common applications of the rare earth elements are summarized in Figure1. The interesting properties that have allowed their application are largely due to the unique 4f electrons that have highly localized electronic states and very predictable electronic transitions that are weakly influenced by the coordination environment or crystal field. In general, this means that the unique physical properties of the rare earth ions are largely unaffected by their surroundings. However, it should be noted that slight variations and nuanced interactions of the rare earth ions with their surroundings are of great research interest [1]. Minerals 2018, 8, 106; doi:10.3390/min8030106 www.mdpi.com/journal/minerals Minerals 2018, 8, 106 2 of 24 Minerals 2018, 8, x FOR PEER REVIEW 2 of 24 Figure 1. Applications of the rare earth elements broken down by element. Most applications are Figure 1. Applications of the rare earth elements broken down by element. Most applications are geared towards high-technology, such as lasers, magnets, phosphors, energy conversion, and geared towards high-technology, such as lasers, magnets, phosphors, energy conversion, and catalysis. catalysis. Adapted from Gschneidner, Jr. [2]. Adapted from Gschneidner, Jr. [2]. The International Union of Pure and Applied Chemistry (IUPAC) defines the rare earth elements as a seriesThe International of 17 chemically Union similar of Pure elements and Applied in the Chemistry periodic (IUPAC)table [3] definesincluding the scandium, rare earth elementsyttrium, asand a seriesthe lanthanides. of 17 chemically Scandium similar and elements yttrium inare the ch periodicemically tablesimilar [3] includingto the lanthanides scandium, and yttrium, often andcollocated the lanthanides. with the lanthanides Scandium in and mineral yttrium deposits. are chemically Scandium similaris not as to widely the lanthanides utilized as and the other often collocatedrare earths with as the the process lanthanides for obtaining in mineral metallic deposits. scandium Scandium is isquite not asdifficult. widely utilizedIt is only as relatively the other rarerecently earths that as thescandium process forhas obtaining found limited metallic applic scandiumation isin quite aluminum difficult. alloys. It is only All relatively but one recently of the thatlanthanides scandium (lanthanum has found to limited lutetium) application fill the 4f in el aluminumection shell. alloys. Depending All but upon one ofclassification the lanthanides and (lanthanumresearchers’ preferences, to lutetium) either fill the lanthanum, 4f election despit shell.e Dependingthe namesake, upon or lutetium classification can be and excluded researchers’ from preferences,the lanthanide either classification. lanthanum, Promethium despite the was namesake, the last or of lutetium rare eart canh elements be excluded to be formally from the lanthanidediscovered classification.and is mainly utilized Promethium for its wasradioactivity the last of in rare research earth and elements a small to amount be formally of applications discovered [4]. and is mainly utilizedThe for rare its earth radioactivity elements in researchare not actually and a small rare amount in geologic of applications abundance, [4 ].despite their name [5] (FigureThe 2). rare In absolute earth elements terms, the are rare not earth actually elemen rarets in are geologic more abundant abundance, than despite many of their the platinum name [5] (Figuregroup metals2). In absolute(e.g., platinum terms, and the rarepalladium) earth elements and have are similar more abundantabundances than to tin, many zinc, of and the platinumtungsten. groupLutetium metals and (e.g., thulium platinum are the and least palladium) abundant and an haved lanthanum, similar abundances cerium, and to tin,yttrium zinc, andare tungsten.the most Lutetiumabundant. andThe thuliumrare earth are element the least of abundant even atomic and lanthanum,number is more cerium, abundant and yttrium than either are the of most the corresponding rare earth elements of odd atomic number on either side (Figure 2) in the periodic table (e.g., cerium (58) is more abundant than both lanthanum (57) and praseodymium (59)). The rare Minerals 2018, 8, 106 3 of 24 abundant. The rare earth element of even atomic number is more abundant than either of the corresponding rare earth elements of odd atomic number on either side (Figure2) in the periodic table (e.g., cerium (58) is more abundant than both lanthanum (57) and praseodymium (59)). The rare earth Minerals 2018, 8, x FOR PEER REVIEW 3 of 24 elements are co-located with one another and usually found as part of a host mineral. Many of these rare earthearth enrichedelements are minerals co-located are with carbonate one another minerals and us [6ually], such found as bastnaesiteas part of a host and mineral. lanthanite, Many and of are foundthese in large rare earth carbonatite enriched deposits, minerals suchare carbonate as those mine at Mountainrals [6], such Pass as bastnaesite (California, and USA) lanthanite, [7] and and Bayan Obo (Innerare found Mongolia, in large China)carbonatite [8,9 ].depos Economicallyits, such as viablethose at rare Mountain earth mineral Pass (California, deposits, USA) large [7] quantities and of mineralsBayan Obo with (Inner high Mongolia, rare earth China) concentrations [8,9]. Economically and chemistries viable rare that earth allow mineral for thedeposits, relatively large easy separationquantities of the of minerals rare earth with elements high rare fromearth concentrations the host, are and mined chemistries and refined that allow in only for the a fewrelatively locations easy separation of the rare earth elements from the host, are mined and refined in only a few locations around the world. Large capital costs, high environmental impact, and specific mineral chemistries around the world. Large capital costs, high environmental impact, and specific mineral chemistries have resultedhave resulted in China in China producing producing the the majority majority of of the the world’sworld’s rare rare earths earths [5,10–14]. [5,10–14 ]. (a) (b) Figure 2. (a) Crustal abundances of the rare earth elements (REEs) relative to silicon (adapted from FigureUSGS 2. (a [5])) Crustal and each abundances other (adapted of the from rare Gupta earth [15]). elements (b) REEs (REEs) are relatively relative abundant to silicon compared (adapted to from USGSpalladium [5]) and eachgroup other metals (adapted (e.g., palladium, from Gupta platinum, [15]). and (b rhodium).) REEs are relatively abundant compared to palladium group metals (e.g., palladium, platinum, and rhodium). Minerals 2018, 8, 106 4 of 24 The ability to refine and produce rare earth products from the aforementioned carbonate mineral deposits begins with a fundamental understanding of the rare earth carbonates. The rare earth carbonates include both the rare earth bearing carbonate minerals and the synthetic rare earth carbonates that match the chemical composition of either the naturally occurring minerals or the pure single element carbonates. Understanding the behavior of the rare earth carbonates in geochemical systems begins with the behavior of the rare earths in the RE2O3-CO2-H2O ternary system. At standard temperature and pressure (25 ◦C, 1 atm), the rare earth carbonates are the hydrated normal rare earth carbonates (RE2(CO3)3·xH2O) and the rare earth hydroxycarbonates (RE(OH)CO3·xH2O, also known as basic carbonates, carbonate hydroxide, hydroxylcarbonates, and hydroxocarbonates). Anhydrous variants of the normal carbonates and hydroxycarbonates exist, but they readily absorb water to create their respective hydrated variants. The rare earth oxycarbonates are also an important class of rare earth carbonates.
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