1. Acid-Base Preparation Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

2. 7/14/2015 Acid-Base Preparation Most common acids and bases are prepared from gases and salts in a series of displacement or redox reactions. common acids and bases production specialty acids

3. 7/14/2015 Common Concentrated Acids 12 M HCl glacial CH 3 COOH 18 M H 2 SO 4 15.6 M HNO 3 mineral acids

4. 7/14/2015 Sulfuric Acid 98%, 18 M S + O 2 SO 2 SO 3 catalyst O 2 SO 3 + H 2 O H 2 SO 4 H 2 SO 4 + SO 3 2 H 2 SO 4 98% concentrated sulfuric acid H 2 SO 4 + SO 3 2 H 2 S 2 O 7 100% fuming sulfuric acid “oleum” pyrosulfuric acid

5. 7/14/2015 Sulfuric Acid 18 M excellent dehydrating agent low oxidizing power except when concentrated sulfate ion is a poor coordinating ligand C 12 H 22 O 11 + H 2 SO 4 12 C + 11 H 2 O

6. 7/14/2015 Hydrochloric Acid 12 M low oxidizing power chloride can act as a coordinating ligand 2 NaCl + H 2 SO 4 Na 2 SO 4 + 2 HCl(g)

7. 7/14/2015 Hydrofluoric Acid Production 48 wt% in water (99% pure) can be redistilled to give 99.9%. Shipped in steel containers or polyethylene lined bottles. CaF 2 (s) + H 2 SO 4 (ℓ)CaSO 4 (s) + 2 HF(g) Δ

8. 7/14/2015 Hydrofluoric Acid Uses Manufacture of chlorofluorcarbons (refrigeration) Synthetic cryolite (aluminum production) Uranium processing (UF 6 ) Alkylation catalysts (superacids) Stainless steel (pickling) Glass etching and frosting 6 HF(aq) + SiO 2 (s)2 H 3 O + (aq) + SiF 6 2- (aq) Fluoridation – water (NaF) & toothpaste (SnF 2 )

9. 7/14/2015 Hydrofluoric Acid Safety HF burns – delayed onset of discomfort - white lesions, painful - dehydration, low pH - F - removes Ca 2+ from tissue forming CaF 2 - insoluble CaF 2 results in - slow healing - excess K + in tissue - excess K + over stimulates nerves Treatment immersion in cold MgSO 4 injection of 10% calcium glutonate surgical excision of lesion

10. 7/14/2015 Nitric Acid 15 M, 70% by weight excellent oxidizing acid NH 3 NONO 2 air H 2 O air Pt air or O 2 H 2 O HNO 3 colorless 4 HNO 3 4 NO 2 + 2 H 2 O + O 2 brown h

11. 7/14/2015 Chloric Acid oxidizing acid 3 Cl 2 (g) + 3 H 2 O5 HCl + HClO 3 (aq) +5

12. 7/14/2015 Sodium Hydroxide Production –Diaphragm or Membrane Cell brine solution concentrated 2 NaOH(aq) + H 2 (g) + Cl 2 (g) 2 NaCl(aq) + 2 H 2 O(ℓ) electrolysis brine → Cl 2 H2H2 → NaOH/NaCl porous diaphragm or membrane steel cathode titanium anode

13. 7/14/2015 Sodium Hydroxide Production – Mercury Cathode Cell brine solution concentrated Cl 2 (g) + 2 Na(Hg)2 NaCl(aq) electrolysis H2OH2O NaOH Cl 2 brine → Na(Hg) titanium anode Mercury cathode brine mercury →

14. 7/14/2015 Ammonia N 2 (g) + 3 H 2 (g)2 NH 3 (g) Fe 400 °C ~200 atm

15. 7/14/2015 Aqua Regia 3 parts HCl 1 parts HNO 3 contains free Cl 2 and NOCl nitrosyl chloride attacks Au, Pt Cl - stabilizes metal complexes AuCl 4 -, PtCl 6 2-

16. 7/14/2015