Lecture 8 September 25, 2009 Ionic Crystals; Born-Haber Cycle

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1 Welcome to Lecture 8 September 25, 2009 Ionic Crystals; BornHaber Cycle

2 Image by MIT OpenCourseWare.

3 Properties of Ionic Crystals solid at room temperature high melting points & boiling points transparent to visible light electrical insulators hard & brittle soluble in water & other polar solvents melt to form ionic liquids (useful in electrolytic extraction of metals) where to search for ionicity???

4 s 1 Hydrogen [He]2s 1 Lithium 1 IA IA [Ne]3s 1 Sodium [Ar]4s 1 Potassium [Kr]5s 1 Rubidium [Xe]6s 1 Cesium ( ) [Rn]7s 1 Francium 1 H 1 3 Li 1 11 Na 1 19 K 1 37 Rb 1 55 Cs 1 87 Fr [He]2s 2 Beryllium [Ne]3s 2 Magnesium [Ar]4s 2 Calcium [Kr]5s 2 Strontium [Xe]6s 2 Barium ( ) 700 < [Rn]7s 2 Radium 2 IIA IIA 4 Be 2 12 Mg 2 20 Ca 2 38 Sr 2 56 Ba 2 88 Ra 2 3 IIIA IIIB [Ar]3d 14s2 Scandium [Kr]4d 15s2 Yttrium * [Xe]5d 16s2 Lanthanum ( ) [Rn]6d 17s2 Actinium 21 Sc 3 39 Y 3 57 La 3 89 ** Ac [Ar]3d 24s2 Titanium IVA IVB [Kr]4d 25s2 Zirconium Hf [Xe]4f 145d26s2 Hafnium (261) 104 Rf 4 [Rn]5f 146d27s2 Rutherfordium** VA VIA VIIA VIIIA VB VIB VIIB VIII , ,3,4, ,3, ,3,4,6, V Cr Mn Fe 2,3 [Ar]3d 34s2 [Ar]3d 54s1 [Ar]3d 54s2 [Ar]3d 64s2 Vanadium Chromium Manganese Iron ( ) Nb 3,5 2,3,4,5,6 Mo Tc 7 2,3,4,6,8 Ru [Kr]4d 45s1 [Kr]4d 55s1 [Kr]4d 55s2 [Kr]4d 75s1 Niobium Molybdenum Technetium Ruthenium Ta 5 2,3,4,5,6 1,2,4,6,7 2,3,4,6,8 W Re Os [Xe]4f 145d36s2 Tantalum [Xe]4f 145d46s2 Tungsten [Xe]4f 145d56s2 Rhenium [Xe]4f 145d66s2 Osmium (262) (263) (262) (265) Bh Db Sg Hs [Rn]5f 146d37s2 [Rn]5f 146d47s2 [Rn]5f 146d57s2 [Rn]5f 146d57s2 Dubnium** Seaborgium** Bohrium** Hassium** Ti Zr [Ar]3d 74s2 Cobalt [Kr]4d 85s1 Rhodium VIIIA VIII [Xe]4f 145d76s2 Iridium Co 2,3 Ni [Ar]3d 84s2 Nickel Rh 2,3,4 Pd 2, [Kr]4d 10 Palladium ,3,4, Ir Pt 9.0 (266) [Rn]5f 146d77s2 Meitnerium** Mt [Xe]4f 145d96s1 Platinum (269) 10 VIIIA VIII 110 Uun [Rn]5f 146d97s1 Ununnilium , Cu 1, [Ar]3d 104s1 Copper [Kr]4d 105s1 Silver , Au 1, [Xe]4f 145d106s1 Gold (272) 11 IB IB 47 Ag Uuu [Rn]5f 146d107s1 Unununium % [Ar]3d 104s2 Zinc [Kr]4d 105s2 Cadmium [Xe]4f 145d106s2 Mercury (277) 12 IIB IIB 30 Zn 2 48 Cd 2 80 Hg 1,2 112 Uub [Rn]5f 146d107s2 Ununbium [He]2s 2p1 Boron [Ne]3s 2p1 Aluminum [Ar]3d 104s2p1 Gallium [Kr]4d 105s2p1 Indium [Xe]4f 145d106s2p1 Thallium 13 IIIB IIIA Ununtrium 5 B 3 13 Al TP 3825 SP [He]2s 2p2 Carbon Ge [Ar]3d 104s2p2 Germanium Sn 2, [Kr]4d 105s2p2 Tin , Pb 2, [Xe]4f 145d106s2p2 Lead Ga 3 In 3 Tl 113 Uut (285) 14 IVB IVA [Ne]3s 2p2 Silicon 6 2, 4 C 14 Si Uuq [Rn]5f 146d107s27p2 Ununquadium TP 614 SP o C [Ar]3d 104s2p3 Arsenic o C [Kr]4d 105s2p3 Antimony As 3,5 Se Br Kr [Ar]3d 104s2p4 [Ar]3d 104s2p3 [Ar]3d 104s2p5 Selenium Bromine Krypton Sb Te 1,5,7 I Xe [Kr]4d 105s2p4 [Kr]4d 105s2p5 [Kr]4d 105s2p6 Tellurium Iodine Xenon ( ) ( ) ( ) Bi Po 2,4 1,3,5,7 At Rn [Xe]4f 145d106s2p4 Polonium [Xe]4f 145d106s2p5 Astatine [Xe]4f 145d106s2p6 Radon [Xe]4f 145d106s2p3 Bismuth 15 VB VA [He]2s 2p3 Nitrogen [Ne]3s 2p3 Phosphorus 115 Uup Ununpentium 7 2, 3,4,5 N 15 3,4,5 P (289) 16 VIB VIA [He]2s 2p4 Oxygen [Ne]3s 2p4 Sulfur 8 O ,4,6 S 116 Uuh [Rn]5f 146d107s27p4 Ununhexium 17 VIIB VIIA [He]2s 2p5 Fluorine [Ne]3s 2p5 Chlorine 117 Uus Ununseptium 9 F ,3,5,7 Cl 18 VIII 0 4, atm s 2 Helium [He]2s 2p6 Neon [Ne]3s 2p6 Argon (293) 2 He 10 Ne 18 Ar 118 Uuo [Rn]5f 146d107s27p6 Ununoctium * ** Ce 3,4 [Xe]4f 15d16s2 Cerium Th 4 [Rn]6d 27s2 Thorium [Xe]4f 36s2 Praseodymium [Rn]5f 26d17s2 Protactinium Pr 3, Nd 3 [Xe]4f 46s2 Neodymium ,4,5, Pa 4, U [Rn]5f 36d17s2 Uranium ( ) [Xe]4f 56s2 Promethium ( ) [Rn]5f 46d17s2 Neptunium 61 Pm Sm 2,3 [Xe]4f 56s2 Samarium ( ) ,4,5, ,4,5, Pu [Rn]5f 67s2 Plutonium Np [Xe]4f 76s2 Europium ( ) [Rn]5f 77s2 Americium 63 Eu 2,3 95 3,4,5,6 Am [Xe]4f 75d16s2 Gadolinium ( ) [Rn]5f 76d17s2 Curium 64 Gd 3 96 Cm [Xe]4f 96s2 Terbium ( ) [Rn]5f 97s2 Berkelium 65 Tb 3,4 97 Bk 3, [Xe]4f 106s2 Dysprosium ( ) [Rn]5f 107s2 Californium 66 Dy 3 98 Cf [Xe]4f 116s2 Holmium ( ) [Rn]5f 117s2 Einsteinium 67 Ho 3 99 Es [Xe]4f 126s2 Erbium ( ) [Rn]5f 127s2 Fermium 68 Er Fm Tm 2,3 [Xe]4f 136s2 Thulium (258.10) [Rn]5f 137s2 Mendelevium [Xe]4f 146s2 Ytterbium ( ) Md 2,3 No 2, [Rn]5f 147s2 Nobelium 70 Yb 2, [Xe]4f 145d16s2 Lutetium (252.11) 1627 [Rn]5f 146d17s2 Lawrencium 71 Lu Lr 3 Image by MIT OpenCourseWare.

5 1 1A H + H Hydride 2 2A 13 3A 14 4A 15 5A 16 6A 17 7A 18 8A Li + Be 2+ N 3 O 2 Nitride Oxide F Fluoride Na + Mg 2+ Al 3+ S 2 Sulfide Cl Chloride K + Ca 2+ Ga 3+ Se 2 Selenide Br Bromide Rb + Sr 2+ In 3+ Sn 2+ Sn 4+ Te 2 I Telluride Iodide Cs + Ba 2+ Tl + Pb 2+ Tl 3+ Pb 4+ Image by MIT OpenCourseWare.

6 Max Born Biography Max Born Biography Max Born was born in Breslau on the 11th December, 1882, to Professor Gustav Born, anatomist and embryologist, and his wife Margarete, nee Kauffmann, who was a member of a Silesian family of industrialists. `.. Max attended the Konig Wilhelm's Gymnasium in Breslau and continued his studies at the Universities of Breslau (where the wellknown mathematician Rosanes introduced him to matrix calculus), Heidelber, Zurich (here he was deeply impressed by Hurwitz's lectures on higher analysis), and Gottingen. In the latter seat of learning he read mathematics chiefly, sitting under Klein, Hilbert, Minkowski, and Runge, but also studied astronomy under Schwarzschild, and physics under Voigt. He was awarded the Prize of the Philosophical Faculty of the University of Gottingen for his work on the stability of elastic wires and tapes in 1906, and graduated at this university.... Image by MIT OpenCourseWare.

7 Fritz Haber Biography Fritz Haber was born on December 9, 1868 in Breslau, Germany, in one of the oldest families of the town, as the son of Siegfried Haber, a merchant. He went to school at the St. Elizabeth classical school at Breslau and he did, even while he was at school, many chemical experiments. From 1886 until 1891 he studied chemistry at the University of Heidelberg under Bunsen, at the University of Berlin under A.W. Hoffmann, and at the Technical School at Charlottenberg under Liebermann. After completing his University studies he voluntarily worked for a time in his father's chemical business and, being interested in chemical technology, he also worked for a while under Professor Georg Lunge at the Institute of Technology at Zurich. He then finally Image by MIT OpenCourseWare.

8 Group Classifications Allotropic Form 13 Symbol Covalent Radius 14,A Metallic Radius [Van der Waals Radius] 15, A Atomic Volume 16 cm 3 /mol Z 17 eff /Polarizability 18 Mn / VIIA VIIB Ωm at 25 o C Crystal Structure 12 Acid/Base Properties 11 Enthalpy of Fusion 20, kj/mol Enthalpy of Vaporization 21, kl/mol (at boiling point) Terminal Conductivity 24 W/cm/K (at 25 o C) Enthalpy of Atomization 22, kl/mol (at 25 o C) Specific Heat Capacity 23 J/g/K (at 25 o C & 100 kpa) H Sublimation Image by MIT OpenCourseWare.

9 Na / = H sublimation Image by MIT OpenCourseWare.

10 3. Na(g) Na + (g) + e _ kj/mol 4. Cl(g) + e _ Cl _ (g) kj/mol _ 1 2 Cl 2 (g) Cl(g) Na(g) Na(g) 122 kj/mol kj/mol 5. Na + (g) + Cl _ (g) NaCl (s) 787 kj/mol Net reaction _ Na(s) Cl 2 (g) NaCl (s) 411 kj/mol A Born _ Haber Cycle for NaCl Image by MIT OpenCourseWare.

11 Cation Li+ Na+ K+ Be 2 + Mg 2 + Ca 2 + Al 3 + Anion F _ Cl _ Br _ I _ O 2_ Lattice energies of some Ionic solids (kj/mol) Image by MIT OpenCourseWare.

13 o Ionic Radii (A) for Ions with Noblegas Electron Configurations Na Mg Al F 1.33 [Ne] [He] [Kr] Rb Sr Y Se Br 1.96 Li Be K Ca Sc S CI 1.81 [Ar] [Xe] Cs Ba La Cs Ba La Te I 2.19 Te I 2.19 Image by MIT OpenCourseWare.

14 Image by MIT OpenCourseWare.

15 2 Al e 2 Al 3 O O e 3 O C 1.5 CO e consumable carbon anode 0.45 kg C / kg Al

16 aluminum produced by electrolytic reduction of Al 2 O 3 world capacity: ~40 million tonnes/year 1886 Charles Martin Hall, USA Paul L.T. Héroult, France decompose Al 2 O 3 dissolved in Na 3 AlF 6 (T = 960 C) liquid Al () and CO 2 (+) find an inert anode source unknown. All rights reserved. This image is excluded from our Creative Commons license. For more information, see

17 2 Al e 2 Al 3 O O e 3 O C 1.5 CO e inert anode no CO2; no CF4

20 MIT OpenCourseWare SC Introduction to Solid State Chemistry Fall 2009 For information about citing these materials or our Terms of Use, visit:

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