1. Ch 11. Group 1 (Alkali Metals)

2. 2  H vap (in kJ/mol) for Metals

3. 3 Elemental Metals Synthesis by electrolysis 2 KOH  K (m) + ½ O 2 (g) + H 2 O (l) Sir Humphrey Davy, 1807 (K, Na) Reactivities: M (m) + H 2 O  MOH (aq) + ½ H 2 (g) Li is rapid; Na to Cs is increasingly violent, explosive

4. 4 Elemental properties

5. 5 Pourbaix s-block

6. 6 Born-Haber approach

7. 7 Solution and lattice enthalpies

8. 8 Exchange / Displacement Large ion salt + small ion salt is better than two salts with large and small ions combined. Example: SaltΔH L sum CsF750 NaI705 1455 kJ/mol CsI620 NaF926 1546 This can help predict some reactions like displacements, ion exchange, thermal stability.

9. 9 Crown ethers and cryptands Formation constants with alkali metal cations [M(OH 2 ) n ] + + ether = [M(ether)] + + n H 2 O KfKf

10. 10 Alkides, electrides 2 Na(s) Na + (solv) + Na - (solv) Na + (solv) [Na(crypt)] + Na - (s) en = ethylenediammine, H 2 NCH 2 CH 2 NH 2 en N2N2 2,2,2 crypt ΔH rxn = 2ΔH at (Na) + I(Na) – E a (Na) + ΔH solv, cation + ΔH solv, anion sodide anion = 2(108) + 514 - 52 + ? + ? ? We know that ΔH hyd (Na + ) = - 400 kJ/mol

11. 11 Electrides [Cs(18-C-6) 2 ] + e - Cs(15-C-5) 2 Cs + is the green sphere, electride anion is pink

12. 12 Li clusters

13. Ch 12. Group 2 (Alkaline Earths)

14. 14 Element properties

15. 15 Be compounds

16. 16 Organo Be compounds

17. 17 Organometallics synthesis Hg(CH 3 ) 2 + Be (s) → Be(CH 3 ) 2 + Hg (l) transmetallation BuLi + BeCl 2 → Bu 2 Be + 2 LiCl (s) halogen exchange BuCl + 2 Li(s) → BuLi + LiCl (s) lithiation BuLi + C 6 H 6 → LiC 6 H 5 + C 4 H 10 Mg(s) + RX → 2 RMgX insertion (Grignard) insertion R 2 Be + 2 MgCl 2 (s) BeCl 2

18. 18 Thermal stability of metal carbonates An important industrial reaction involves the thermolysis of metal carbonates to form metal oxides according to: MCO 3 (s) → MO (s) + CO 2 (g)  G must be negative for the reaction to proceed. At the lowest reaction temp:  G = 0 and T min =  H /  S  S is positive because gas is liberated. As T increases,  G becomes more negative (i.e. the reaction becomes more favorable).  S depends mainly on  S 0 {CO 2 (g)} and is almost independent of M.

19. 19 Thermal stability of metal carbonates MCO 3 (s) → MO (s) + CO 2 (g) T min almost directly proportional to  H.  H L favors formation of the oxide (smaller anion) for smaller cations. So T min for carbonates should increase with cation size.

20. 20 Carbonate stabilities

21. 21 Mg 2+ chelation with EDTA EDTA = ethylenediaminetetraacetate