The Lightest Metals

Science and Technology from Lithium to Calcium
 
 
Wiley (Verlag)
  • erschienen am 19. November 2015
  • |
  • 496 Seiten
 
E-Book | ePUB mit Adobe DRM | Systemvoraussetzungen
978-1-118-75144-2 (ISBN)
 
The first seven metals in the periodic table are lithium, beryllium, sodium, magnesium, aluminium, potassium and calcium, known collectively as the "lightest metals". The growing uses of these seven elements are enmeshing them ever more firmly into critical areas of 21st century technology, including energy storage, catalysis, and various applications of nanoscience.
This volume provides comprehensive coverage of the fundamentals and recent advances in the science and technology of the lightest metals. Opening chapters of the book describe major physical and chemical properties of the metals, their occurrence and issues of long-term availability. The book goes on to disucss a broad range of chemical features, including low oxidation state chemistry, organometallics, metal-centered NMR spectroscopy, and cation-pi interactions. Current and emerging applications of the metals are presented, including lithium-ion battery technology, hydrogen storage chemistry, superconductor materials, transparent ceramics, nano-enhanced catalysis, and research into photosynthesis and photoelectrochemical cells.
The content from this book will be added online to the Encyclopedia of Inorganic and Bioinorganic Chemistry: http://www.wileyonlinelibrary.com/ref/eibc
1. Auflage
  • Englisch
  • New York
  • |
  • Großbritannien
John Wiley & Sons
  • 33,68 MB
978-1-118-75144-2 (9781118751442)
1118751442 (1118751442)
weitere Ausgaben werden ermittelt
Contributors XI
Series Preface XV
Volume Preface XVII
PART 1: BACKGROUND 1
Interrelationships between the Lightest Metals 3
Nicholas C. Boyde and Timothy P. Hanusa
Occurrence and Production of Beryllium 23
Stephen Freeman
Occurrence of Magnesia Minerals and Production of Magnesium Chemicals and Metal 35
Mark A. Shand
Occurrence and Production of Aluminum 47
Halvor Kvande
Status as Strategic Metals 57
Deborah A. Kramer
Resource Sustainability 67
David A. Atwood
PART 2: FUNDAMENTALS 71
Low Oxidation State Chemistry 73
Michael S. Hill
Solution NMR of the Light Main Group Metals 91
Timothy P. Hanusa
Solid-State NMR of the Light Main Group Metals 117
Robert W. Schurko and Michael J. Jaroszewicz
Cation-pi Interactions 173
Yi An and Steven E. Wheeler
Ion Channels and Ionophores 185
Peter J. Cragg
Beryllium Metal Toxicology: A Current Perspective 205
Terence M. Civic
PART 3: APPLICATIONS 211
Reimagining the Grignard Reaction 213
Sven Krieck and Matthias Westerhausen
Aryllithiums and Hetaryllithiums: Generation and Reactivity 231
D. W. Slocum
Magnesium and Calcium Complexes in Homogeneous Catalysis 255
Merle Arrowsmith
Aluminum-Based Catalysis 281
Mark R. Mason
Lithium-Ion Batteries: Fundamentals and Safety 303
Isidor Buchmann
Li-Ion Batteries and Beyond: Future Design Challenges 315
Yoon Hwa and Elton J. Cairns
High-Pressure Synthesis of Hydrogen Storage Materials 335
Hiroyuki Saitoh, Shigeyuki Takagi, Katsutoshi Aoki and Shin-ichi Orimo
Processing and Applications of Transparent Ceramics 343
Ling Bing Kong, Yizhong Huang, Zhili Dong, Tianshu Zhang, Wenxiu Que, Jian Zhang, Dingyuan Tang and Sean Li
Light-Element Superconductors 371
Andreas Hermann
One-dimensional Nanostructure-enhanced Catalysis 387
Sibo Wang, Zheng Ren, Yanbing Guo and Pu-Xian Gao
Lithium Pharmacology 417
Philip G. Janicak and Bradley R. Cutler
Solar Energy and Photovoltaics 427
Arnulf Jäger-Waldau
Abbreviations and Acronyms 437
Index 441

Interrelationships between the Lightest Metals


Nicholas C. Boyde and Timothy P. Hanusa

Vanderbilt University, Nashville, TN, USA

  1. 1 Introduction
  2. 2 Nucleosynthesis and Abundance of the Lightest Metals
  3. 3 Discovery, Initial Isolation, and Commercial Production
  4. 4 Isodiagonal Relationships
  5. 5 Solid-State Structures of the Metals
  6. 6 Comparative Physical Properties
  7. 7 Ceramics, Glasses, and Alloys
  8. 8 Conclusions
  9. 9 Acknowledgment
  10. 10 Glossary
  11. 11 Related Articles
  12. 12 Abbreviations and Acronyms
  13. 13 References

1 Introduction


Use of the expression "the lightest metals" requires some explanation, especially because the terms "light metals" and "heavy metals", although often encountered in chemical and engineering contexts, are not uniquely defined. Magnesium, aluminum, and titanium (and sometimes beryllium) are traditionally considered among the "light metals" in metallurgical settings, and they are indeed "light" if measured by density (grams per cubic centimeter) as compared to iron or copper (e.g., Mg is only 22% as dense as Fe). However, the use of density alone as a classifier leads to some awkward groupings. For example, yttrium has nearly the same density as titanium (both about 4.5 g cm-3), and barium (3.5 g cm-3) is less dense than either, but neither Y nor especially Ba is ever counted among the "light" metals [with some irony, the name barium, despite the element's low density, comes from the Greek barys, meaning "heavy"; the heaviness refers to the oxide, BaO (5.7 g cm-3), not the metal itself]. Consequently, the "lightest" metals are defined here as those pretransition metals of lowest atomic number; that is, lithium, beryllium, sodium, magnesium, aluminum, potassium, and calcium (atomic no. 3-20). Although they indeed possess relatively low density, they are not a set of the least dense metals in the periodic table [elemental cesium (1.9 g cm-3), e.g., is only 70% as dense as aluminum (2.7 g cm-3)].

Taken as a group, the "lightest metals" are among the most important elements on the Earth and are critical both to life and civilization. Much of their importance stems from their ubiquity: Al is the most abundant metal in the Earth's crust (8.3% by weight) and is a constituent of the widely distributed aluminosilicates such as feldspars, garnets, and kaolin clays.1, 2 The metals Ca, Mg, Na, and K constitute the fifth through eighth most abundant elements in the crust. It is perhaps not surprising that their ions (Ca2+, Mg2+, Na+, and K+) are the most common metal species in biological systems, where they play myriad roles, from the formation of bones to conversion of solar energy through photosynthesis.3, 4 The use of compounds of these metals has been foundational to the development of human society: limestone, marble, and concrete building materials (containing CaCO3, CaO, and MgO) have been associated with cultures from ancient Mesopotamia and China (e.g., in the Great Wall) to the present. The semiprecious lapis lazuli, a mineral whose deep blue color arises from the S3- ions in lazurite, a complex tectosilicate that contains three of the lightest metals (with the formula (Na,Ca)8[(S,Cl,SO4,OH)]2(Al6Si6O24)), has been mined as a gem for at least 6000 years and served as the source of the natural pigment ultramarine since the early European Middle Ages (Figure 1). In the form of alum (KAl(SO4)2·12H2O), aluminum has been used as a mordant in dying cloth for over two millennia.5 The widespread availability of aluminum metal itself at the end of the nineteenth century transformed the modern transportation and building industries, and the aircraft and 100+-story buildings that are known today would not be possible without aluminum and its alloys. Lithium, although far less abundant than sodium or potassium, has become prominently associated with consumer electronics in the form of the lithium-ion battery, powering everything from music players, cell phones, and digital cameras to electric automobiles (see Lithium-Ion Batteries: Fundamentals and Safety). Beryllium, the least abundant of the "lightest" group (although about as common as arsenic), has restricted uses owing to the toxicity of its salts (see Beryllium Metal Toxicology: A Current Perspective), but is a component of widely used copper alloys, and, in the form of emeralds, has been treasured as a precious gemstone for millennia.

Figure 1 Lapis lazuli, the mineral source of the pigment ultramarine, has been used in the arts for millennia; a polished obelisk of the material is behind the natural stone

(By owner's permission)

In the briefest summary, the lightest metals are all lustrous, silvery elements that, with the exception of beryllium, are relatively soft (Mohs hardness 1.5-2.75; that for Be is 5.5, about the same as molybdenum) (see Table 1). The metals are almost never found in the elemental state in nature, as they react in air, and all rapidly form an oxide coating on their surface. The oxide layer of beryllium and aluminum passivates the metals and inhibits further reaction with oxygen or water. The other metals react with water with various degrees of vigor; magnesium reacts with steam, and calcium reacts slowly with cold water. Lithium, sodium, and potassium all float on water and release hydrogen gas as they react with it; in the case of sodium or potassium, the hydrogen will often be ignited from the heat of reaction. With a few important exceptions (see Low Oxidation State Chemistry), the metals all display their "expected" oxidation state in compounds (e.g., +1 for Li and Na, +2 for Be and Mg, and +3 for Al).

Table 1 Atomic and physical properties of the lightest metals

Li Be Na Mg Al K Ca Atomic number 3 4 11 12 13 19 20 No. of naturally occurring isotopes 2 1 1 3 1 3 6 Atomic mass (g mol-1) 6.94 9.01 23.00 24.31 26.98 39.10 40.08 Electron configuration [He]2s1 [He]2s2 [Ne]3s1 [Ne]3s2 [Ne]3s23p1 [Ar]4s1 [Ar]4s2 Ionization energy (kJ mol-1) 520.2 (1st) 899.4 (1st); 1757 (2nd) 495.8 (1st) 737.7 (1st); 1451 (2nd) 577.5 (1st); 1816.7 (2nd); 2744.8 (3rd) 418.8 (1st) 589.8 (1st); 1145.4 (2nd) Metal radius (Å) 1.52 1.12 1.86 1.60 1.43 2.27 1.97 Ionic radius (six-coordination) (Å) 0.76 0.45 1.02 0.72 0.535 1.38 1.00 E° for Mn+(aq) + ne- M(s) (V) -3.05 -1.97 -2.71 -2.36 -1.78 (n = 3) -2.93 -2.84 Melting point (°C) 181 1287 97.7 650 660 63.7 842 Boiling point (°C) 1342 2469 883 1090 2519 759 1484 Density (20 °C) 0.53 1.85 0.97 1.74 2.70 0.86 1.55 ?Hfus (kJ mol-1) 2.93 15 2.64 8.9 10.7 2.39 8.6 ?Hvap (kJ mol-1) 148 309 99 127 294 79 155 Electrical resistivity (20 °C)/µO cm 9.5 3.7 4.89 4.5 2.7 7.4 3.4

Data from Ref. 6.

In this article, various chemical and physical properties of both the elemental and ionic forms of the lightest metals are compared to each other and to the related metals and their compounds. The subject is vast, and specifics can be found in various textbooks.7-9 We highlight here some of the distinctive features of this special group of elements.

2 Nucleosynthesis and Abundance of the Lightest Metals


Nucleosynthesis is the process by which elements in the universe heavier than hydrogen have been generated. The lightest elements are generally thought to have been produced during the "big bang", at the start of the formation of the universe, in the process of big bang nucleosynthesis (BBN).10, 11 The BBN model seeks to explain the genesis...

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