Solutions Manual for Organic Chemistry: An Acid-Base Approach, 2nd Edition – Step-by-Step Problem-Solving Guide and Study Support Resource

SOLUTIONS MANUAL FOR by ORGANIC CHEMISTRY:This study resource is based on Organic Chemistry: An Acid-Base Approach, Second Edition and provides structured guidance to help students understand key problem-solving methods in organic chemistry. It focuses on acid–base concepts, reaction mechanisms, and step-by-step approaches to solving textbook-style questions. The material is designed to support learning and revision by reinforcing core organic chemistry principles such as acidity, basicity, equilibria, and reaction pathways. It is intended as a study aid for students working through coursework, tutorials, and exam preparation. AN ACID-BASE APPROACH, SECOND EDITION Michael B. SmithSOLUTIONS MANUAL FOR by Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business ORGANIC CHEMISTRY: AN ACID-BASE APPROACH, SECOND EDITION Michael B. 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Visit the Taylor & Francis Web site at and the CRC Press Web site at Chapter 02 Solutions Manual Organic Chemistry. An Acid-Base Approach 2nd Edition 27. (a) Nitric acid is a stronger acid than water, so water is the base and nitric acid is the acid in this reaction to generate the nitrate anion (conjugate base) and the hydronium ion (conjugate acid). (b) Water is a stronger acid than ammonia, so ammonia is the base and water is the acid in this reaction. The reaction products are hydroxide anion (conjugate base) and the ammonium ion (conjugate acid). (c) Hydrobromic acid is a stronger acid than ammonia, so ammonia is the base and HBr is the acid in this reaction to generate the bromide anion (conjugate base) and the ammonium ion (conjugate acid). (d) Hydrochloric acid is a stronger acid than water, so water is the base and HCl is the acid in this reaction to generate the chloride anion (conjugate base) and the hydronium ion (conjugate acid). (e) N O O O H OH2 N O O O H3O+ K a = [NO3–] [H3O+] [HNO3] [H2O] H O H NH3 H O H-NH3 K a = [HO–] NH4+] [H2O] [NH3] Br H NH3 Br H-NH3 K a = [Br–] [NH4+] [HBr] [NH3] Cl H OH2 Cl- H3O+ Ka = [Cl-] [H3O+] [HCl] [H2O]Note that the acidic hydrogen atom is attached to a carbon atom. The amide anion is clearly a base, which a very strong base. Therefore, the strong base can react wit the weakly acidic “carbon acid”. In other words, NH2– is the base and chloroform is the acid in this reaction that generates the anion –CCl3 (the conjugate base) and ammonia, NH3, which is the conjugate acid. 28. The main reason is likely the relative size of the bromide ion (182 pm or 1.82 Å) versus the chloride ion (100 pm, or 1.00 Å). Greater charge dispersal for the bromide ion leads to greater stability of that conjugate base, and a larger Ka. 29. In this reaction, water is the base that reacts with the HCl. If water is omitted, the base has been excluded from the equilibrium expression for an acid-base reaction. 30. (a) NH3 (b) H3CO– (c) –NO3 (d) Br– (e) –:NH2 (f) –CH3 31. The ‘ate. complex in the “box” is the reaction product, where N of ammonia is the electron donor (the base). 32. Oxygen is more electronegative than nitrogen, so nitrogen is more electron-rich, and will be a better electron-donor. In addition, the ‘ate’ complex from ammonia is an ammonium salt whereas water will react to form an oxonium salt. The ammonium salt is more stable, which contributes to the overall increased Lewis basicity of the nitrogen atom in ammonia. 33. In these neutral molecules, phosphorus is larger than nitrogen, with covalent radii of 106 and 71 pm (1.06 Å and 0.71 Å), respectively. The charge density of nitrogen is greater. Therefore, ammonia is expected to be the stronger Lewis base. 34. An ate complex is the salt generated by reaction of a Lewis acid with a Lewis base. The atom derived from the Lewis base expands its valence and assumes a positive charge, whereas the atom derived from the Lewis base expand its valence and assumes a negative charge. 35