Chapter 19 Carboxylic Acids

1. Chapter 19Carboxylic Acids

2. 19.1Carboxylic Acid Nomenclature

3. O HCOH O CH3COH O CH3(CH2)16COH Table 19.1 (page 737) • systematic IUPAC names replace "-e" ending of alkane with "oic acid" Systematic Name methanoic acid ethanoic acid octadecanoic acid

4. O HCOH O CH3COH O CH3(CH2)16COH Table 19.1 (page 737) • common names are based on natural origin rather than structure Systematic Name Common Name methanoic acid formic acid ethanoic acid acetic acid octadecanoic acid stearic acid

5. O CH3CHCOH O OH CH3(CH2)7 (CH2)7COH C C H H Table 19.1 (page 737) Systematic Name Common Name 2-hydroxypropanoicacid lactic acid (Z)-9-octadecenoicacid oleic acid

6. 19.2Structure and Bonding

7. Formic acid is planar

8. Formic acid is planar O H C O 120 pm H 134 pm

9. – •• •• R O R O + •• •• •• C C O O •• •• •• •• H H Electron Delocalization

10. – – •• •• •• R O R O R O + •• •• •• •• •• C C C + O O O •• •• •• •• •• H H H Electron Delocalization • stabilizes carbonyl group

11. 19.3Physical Properties

12. OH O O OH 141°C Boiling Points • Intermolecular forces, especially hydrogen bonding, are stronger in carboxylic acids than in other compounds of similar shape and molecular weight bp (1 atm) 31°C 80°C 99°C

13. O O H CCH3 H3CC O H O Hydrogen-bonded Dimers • Acetic acid exists as a hydrogen-bonded dimer in the gas phase. The hydroxyl group of each molecule is hydrogen-bonded to the carbonyl oxygen of the other.

14. Hydrogen-bonded Dimers • Acetic acid exists as a hydrogen-bonded dimer in the gas phase. The hydroxyl group of each molecule is hydrogen-bonded to the carbonyl oxygen of the other.

15. H O O H H3CC H O H O H Solubility in Water • carboxylic acids are similar to alcohols in respect to their solubility in water • form hydrogen bonds to water

16. 19.4Acidity of Carboxylic Acids • Most carboxylic acids have a pKa close to 5.

17. O CH3COH Carboxylic acids are weak acids • but carboxylic acids are far more acidic than alcohols CH3CH2OH Ka = 1.8 x 10-5 pKa = 4.7 Ka = 10-16 pKa = 16

18. O CH3CO– + H+ O CH3COH Free Energies of Ionization CH3CH2O– + H+ DG°= 64 kJ/mol DG°= 91 kJ/mol DG°= 27 kJ/mol CH3CH2OH

19. O RC O d+ – •• •• O O •• •• •• RC RC •• – O O •• •• •• •• Greater acidity of carboxylic acids is attributedstabilization of carboxylate ion by inductive effect of carbonyl group – resonance stabilization of carboxylate ion

20. Figure 19.4: Electrostatic potential maps ofacetic acid and acetate ion Acetic acid Acetate ion

21. 19.5Salts of Carboxylic Acids

22. O O Carboxylic acids are neutralized by strong bases • equilibrium lies far to the right; K is ca. 1011 • as long as the molecular weight of the acid is not too high, sodium and potassium carboxylate salts are soluble in water + + RCOH HO– RCO– H2O strongeracid weakeracid

23. O O CH3(CH2)16CO Micelles • unbranched carboxylic acids with 12-18 carbonsgive carboxylate salts that form micelles inwater ONa sodium stearate(sodium octadecanoate) – Na+

24. O Micelles ONa • sodium stearate has a polar end (the carboxylate end) and a nonpolar "tail" • the polar end is "water-loving" or hydrophilic • the nonpolar tail is "water-hating" or hydrophobic • in water, many stearate ions cluster together to form spherical aggregates; carboxylate ions on the outside and nonpolar tails on the inside polar nonpolar

25. Figure 19.5 (page 744) A micelle

26. Micelles • The interior of the micelle is nonpolar and has the capacity to dissolve nonpolar substances. • Soaps clean because they form micelles, which are dispersed in water. • Grease (not ordinarily soluble in water) dissolves in the interior of the micelle and is washed away with the dispersed micelle.