9: Acid-Base and Donor-Acceptor Chemistry
- Page ID
- 279032
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\(\newcommand{\avec}{\mathbf a}\) \(\newcommand{\bvec}{\mathbf b}\) \(\newcommand{\cvec}{\mathbf c}\) \(\newcommand{\dvec}{\mathbf d}\) \(\newcommand{\dtil}{\widetilde{\mathbf d}}\) \(\newcommand{\evec}{\mathbf e}\) \(\newcommand{\fvec}{\mathbf f}\) \(\newcommand{\nvec}{\mathbf n}\) \(\newcommand{\pvec}{\mathbf p}\) \(\newcommand{\qvec}{\mathbf q}\) \(\newcommand{\svec}{\mathbf s}\) \(\newcommand{\tvec}{\mathbf t}\) \(\newcommand{\uvec}{\mathbf u}\) \(\newcommand{\vvec}{\mathbf v}\) \(\newcommand{\wvec}{\mathbf w}\) \(\newcommand{\xvec}{\mathbf x}\) \(\newcommand{\yvec}{\mathbf y}\) \(\newcommand{\zvec}{\mathbf z}\) \(\newcommand{\rvec}{\mathbf r}\) \(\newcommand{\mvec}{\mathbf m}\) \(\newcommand{\zerovec}{\mathbf 0}\) \(\newcommand{\onevec}{\mathbf 1}\) \(\newcommand{\real}{\mathbb R}\) \(\newcommand{\twovec}[2]{\left[\begin{array}{r}#1 \\ #2 \end{array}\right]}\) \(\newcommand{\ctwovec}[2]{\left[\begin{array}{c}#1 \\ #2 \end{array}\right]}\) \(\newcommand{\threevec}[3]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \end{array}\right]}\) \(\newcommand{\cthreevec}[3]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \end{array}\right]}\) \(\newcommand{\fourvec}[4]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \\ #4 \end{array}\right]}\) \(\newcommand{\cfourvec}[4]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \\ #4 \end{array}\right]}\) \(\newcommand{\fivevec}[5]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \\ #4 \\ #5 \\ \end{array}\right]}\) \(\newcommand{\cfivevec}[5]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \\ #4 \\ #5 \\ \end{array}\right]}\) \(\newcommand{\mattwo}[4]{\left[\begin{array}{rr}#1 \amp #2 \\ #3 \amp #4 \\ \end{array}\right]}\) \(\newcommand{\laspan}[1]{\text{Span}\{#1\}}\) \(\newcommand{\bcal}{\cal B}\) \(\newcommand{\ccal}{\cal C}\) \(\newcommand{\scal}{\cal S}\) \(\newcommand{\wcal}{\cal W}\) \(\newcommand{\ecal}{\cal E}\) \(\newcommand{\coords}[2]{\left\{#1\right\}_{#2}}\) \(\newcommand{\gray}[1]{\color{gray}{#1}}\) \(\newcommand{\lgray}[1]{\color{lightgray}{#1}}\) \(\newcommand{\rank}{\operatorname{rank}}\) \(\newcommand{\row}{\text{Row}}\) \(\newcommand{\col}{\text{Col}}\) \(\renewcommand{\row}{\text{Row}}\) \(\newcommand{\nul}{\text{Nul}}\) \(\newcommand{\var}{\text{Var}}\) \(\newcommand{\corr}{\text{corr}}\) \(\newcommand{\len}[1]{\left|#1\right|}\) \(\newcommand{\bbar}{\overline{\bvec}}\) \(\newcommand{\bhat}{\widehat{\bvec}}\) \(\newcommand{\bperp}{\bvec^\perp}\) \(\newcommand{\xhat}{\widehat{\xvec}}\) \(\newcommand{\vhat}{\widehat{\vvec}}\) \(\newcommand{\uhat}{\widehat{\uvec}}\) \(\newcommand{\what}{\widehat{\wvec}}\) \(\newcommand{\Sighat}{\widehat{\Sigma}}\) \(\newcommand{\lt}{<}\) \(\newcommand{\gt}{>}\) \(\newcommand{\amp}{&}\) \(\definecolor{fillinmathshade}{gray}{0.9}\)- 9.1: Acid-Base Models as Organizing Concepts
- The concept of acids and bases is often associated with the movement of hydrogen ions from one molecule or ion to another. However, a host of acid base concepts have been developed to help chemists organize and make sense of a wide range of reactions
- 9.3: Brønsted-Lowry Concept
- 9.3.1: Rules of Thumb for thinking about the relationship between Molecular Structure and Brønsted Acidity and Basicity*
- 9.3.2: The acid-base behavior of binary element hydrides is determined primarily by the element's electronegativity and secondarily by the element-hydrogen bond strength.*
- 9.3.3: Brønsted-Lowry Superacids and the Hammett Acidity Function
- 9.3.4: Thermodynamics of Solution-Phase Brønsted Acidity and Basicity
- 9.3.5: Thermodynamics of Gas Phase Brønsted Acidity and Basicity
- 9.3.6: The Acidity of an Oxoacid is Determined by the Electronegativity and Oxidation State of the Oxoacid's Central Atom*
- 9.3.7: High Charge to Size Ratio Metal Ions Act as Brønsted Acids in Water
- 9.3.8: The Solvent System Acid Base Concept
- 9.3.9: Acid-Base Chemistry in Amphoteric Solvents and the Solvent Levelling Effect
- 9.3.10: Non-nucleophilic Brønsted-Lowry Superbases
- 9.4: Lewis Concept and Frontier Orbitals
- 9.4.1: The frontier orbital approach considers Lewis acid base reactions in terms of the donation of electrons from the base's highest occupied orbital into the acid's lowest unoccupied orbital.
- 9.4.2: All other things being equal electron withdrawing groups tend to make Lewis acids stronger and bases weaker while electron donating groups tend to make Lewis bases stronger and acids weaker
- 9.4.3: The electronic spectra of charge transfer complexes illustrate the impact of frontier orbital interactions on the electronic structure of Lewis-Acid base adducts.
- 9.4.4: Substances' solution phase Lewis Basicity towards a given acid may be estimated using the enthalphy change for dissociation of its adduct with a reference acid of similar hardness.
- 9.4.5: In the boron triflouride affinity scale the enthalphy change on formation of an adduct between the base and boron triflouride is taken as a measure of Lewis basicity.
- 9.4.6: Lewis base strength may also be estimated by measuring structural or energy changes on formation of a Lewis acid-base complex, as illustrated by efforts to spectroscopically assess of the strengths of halogen bonds
- 9.4.7: Bulky groups weaken the strength of Lewis acids and bases because they introduce steric strain into the resulting acid-base adduct.
- 9.4.8: Frustrated Lewis pair chemistry uses Lewis acid and base sites within a molecule that are sterically restricted from forming an adduct with each other.