Chem 3053

Organic Chemistry I Klein 1st Ed. Chapter 3 Acids and Bases

R.L. Halterman

Acid base reactions are the first reactions we study. The more favorable the loss of a proton, the more acidic the compound is and the greater the energy drop when transferring the proton. We will qualitatively analyze why some compounds lose protons more favorably and the quantitative use of the measure of acidity in quickly determining reaction favorability. Important Concepts, Topics and Reactions: Section 3.1Topic Acids (Bronsted definition) are proton donors. Bases are proton acceptors. Once an acid donates a proton it becomes a conjugate base for the back reaction. Protonated bases are conjugate acids. Electron movement arrows (curved arrows) must be properly used to show flow of electrons from their source to their landing spot. In acid-base reactions of A-H often a an arrow will go from a lone pair to a hydrogen with the A-H bond breaking and depositing a new lp on the Aatom. Problems SB3.1, 3.1, 3.2 The quantitative treatment of Bronsted acidity uses the equilibrium constant for transferring a proton from AH to water. The equilibrium constant for this reaction uses Ka = Keq[H2O]. The Ka for this process ranges from 1010 (very favorable) to 10-50 (very unfavorable) and is expressed as pKa from -10 (strongly acidic) to 50 (very weakly acidic). The favorability of acid base reactions between non-water acids/bases can still be assessed using the pKas of the species involved. The stronger acid will favorably deposit its proton on a base to produce a weaker acida process whose favorability is determined by the difference in the pKas of the starting and ending acid forms. You should know the pKa values in Table 3.1. Problems SB3.2, 3.4, SB3.3, 3.7, 3.9, SB3.4, 3.10, Qualitative analysis of acidity means analyzing the energetic favorability of the reaction (transfer of a proton). In practice it generally comes down to the stability of the electrons between the donor atom and the proton (A-H bond) before reaction and the stability of the non-bonded electrons left on the donor atom (A:). The change in stability /reaction favorability usually depends more on the stability of resulting lone pair. Four factors can be evaluated to assess stability of the lone pair (ARIO: which atom (more ENC or larger size), any resonance stabilization, any inductive stabilization or which orbital (hybridization stabilization)). When comparing two acids first determine if the donating atom is differentif so you just need to analyze ENC/size differences. If the donating atoms in the comparison are the same you need to analyze for differences in resonance, induction and hybridization. [This section is one of the most important of the course]. Problems. SB3.5, 3.13, 3.14, SB3.6, 3.15, SB3.7, 3.19, SB3.8, 3.22, SB3.9, 3.25, 3.26, 3.28 Choosing reagents and driving acid-base equilibrium comes down to insuring that the desired deprotonation is energetically more favorable. Using a stronger base (unstable electron lone pair in B:) will produce a weaker conjugate acid (more stable electrons in B-H bond) and thus be able to convert A-H to A:. In practice choose a base whose conjugate acid has higher pKa than the compound you wish to deprotonate. Problems SB3.10, 3.29, SB3.11, 3.31 Acid-base reactions can be limited by solvent. Since water has a pKa of 15.7, we cannot use bases whose conjugate acid is much weaker than this (eg amide H2N would react with H2O to make NH3 with pKa of 38). Thus, putting a strong base in water will simply deprotonate water and level the base strength to that of water/hydroxide. Strong bases must therefore be used in

3.2

3.3

3.4

3.5

3.6

non-protic or aprotic solvents (protic solvent most often means O-H bonds in solvent molecule such as H2O or alcohols or carboxylic acids). Common aprotic solvents would be alkanes or ethers. 3.7 Solvent can help stabilize anions. More polar or hydrogen bonding solvents better stabilize anionic compounds. Anions that allow better access to stabilizing solvent will be more stable (eg ethanol more acidic than tert-butanol because resulting ethoxide anion allows for more solvation of the anionic oxygen atom). Again we see that stability of anion resulting from deprotonation determines favorability of deprotonation/acidity. Counterions are always present. Cations such as Na+ or K+ are often not closely associated or bound to the anion. Such spectator ions can be asked to sit down to give you a better view of the reaction (ie do not show them or move these cations aside to show the anionic form with its charge). Although they are usually safely ignored, later on in some limited cases, they can play a non-spectator role. Thus, it is usually clearer not to depict these distracting counterions, but keep in mind that they are there and could be brought back into view if an explanation or results do not make sense without them. Lewis Acids and Bases. Lewis acids are electron acceptors and Lewis bases are electron donors. Common examples include metals (Lewis acid) coordinated to oxygen lone pairs of electrons (Lewis base). Problems: SB3.12, 3.34.

3.8

3.9

Review concepts and terminology p. 128-129 and SkillBuilder concepts p. 129-132. Assigned Problems for End of Unit Do these problems when you have finished the chapter (or as indicated in lecture). 3.36, 3.37, 3.41, 3.43, 3.44, 3.45, 3.46, 3.47, 3.49, 3.52