6: Acid-Base and Donor-Acceptor Chemistry
- Page ID
- 151393
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\(\newcommand{\avec}{\mathbf a}\) \(\newcommand{\bvec}{\mathbf b}\) \(\newcommand{\cvec}{\mathbf c}\) \(\newcommand{\dvec}{\mathbf d}\) \(\newcommand{\dtil}{\widetilde{\mathbf d}}\) \(\newcommand{\evec}{\mathbf e}\) \(\newcommand{\fvec}{\mathbf f}\) \(\newcommand{\nvec}{\mathbf n}\) \(\newcommand{\pvec}{\mathbf p}\) \(\newcommand{\qvec}{\mathbf q}\) \(\newcommand{\svec}{\mathbf s}\) \(\newcommand{\tvec}{\mathbf t}\) \(\newcommand{\uvec}{\mathbf u}\) \(\newcommand{\vvec}{\mathbf v}\) \(\newcommand{\wvec}{\mathbf w}\) \(\newcommand{\xvec}{\mathbf x}\) \(\newcommand{\yvec}{\mathbf y}\) \(\newcommand{\zvec}{\mathbf z}\) \(\newcommand{\rvec}{\mathbf r}\) \(\newcommand{\mvec}{\mathbf m}\) \(\newcommand{\zerovec}{\mathbf 0}\) \(\newcommand{\onevec}{\mathbf 1}\) \(\newcommand{\real}{\mathbb R}\) \(\newcommand{\twovec}[2]{\left[\begin{array}{r}#1 \\ #2 \end{array}\right]}\) \(\newcommand{\ctwovec}[2]{\left[\begin{array}{c}#1 \\ #2 \end{array}\right]}\) \(\newcommand{\threevec}[3]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \end{array}\right]}\) \(\newcommand{\cthreevec}[3]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \end{array}\right]}\) \(\newcommand{\fourvec}[4]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \\ #4 \end{array}\right]}\) \(\newcommand{\cfourvec}[4]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \\ #4 \end{array}\right]}\) \(\newcommand{\fivevec}[5]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \\ #4 \\ #5 \\ \end{array}\right]}\) \(\newcommand{\cfivevec}[5]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \\ #4 \\ #5 \\ \end{array}\right]}\) \(\newcommand{\mattwo}[4]{\left[\begin{array}{rr}#1 \amp #2 \\ #3 \amp #4 \\ \end{array}\right]}\) \(\newcommand{\laspan}[1]{\text{Span}\{#1\}}\) \(\newcommand{\bcal}{\cal B}\) \(\newcommand{\ccal}{\cal C}\) \(\newcommand{\scal}{\cal S}\) \(\newcommand{\wcal}{\cal W}\) \(\newcommand{\ecal}{\cal E}\) \(\newcommand{\coords}[2]{\left\{#1\right\}_{#2}}\) \(\newcommand{\gray}[1]{\color{gray}{#1}}\) \(\newcommand{\lgray}[1]{\color{lightgray}{#1}}\) \(\newcommand{\rank}{\operatorname{rank}}\) \(\newcommand{\row}{\text{Row}}\) \(\newcommand{\col}{\text{Col}}\) \(\renewcommand{\row}{\text{Row}}\) \(\newcommand{\nul}{\text{Nul}}\) \(\newcommand{\var}{\text{Var}}\) \(\newcommand{\corr}{\text{corr}}\) \(\newcommand{\len}[1]{\left|#1\right|}\) \(\newcommand{\bbar}{\overline{\bvec}}\) \(\newcommand{\bhat}{\widehat{\bvec}}\) \(\newcommand{\bperp}{\bvec^\perp}\) \(\newcommand{\xhat}{\widehat{\xvec}}\) \(\newcommand{\vhat}{\widehat{\vvec}}\) \(\newcommand{\uhat}{\widehat{\uvec}}\) \(\newcommand{\what}{\widehat{\wvec}}\) \(\newcommand{\Sighat}{\widehat{\Sigma}}\) \(\newcommand{\lt}{<}\) \(\newcommand{\gt}{>}\) \(\newcommand{\amp}{&}\) \(\definecolor{fillinmathshade}{gray}{0.9}\)- 6.1: 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
- 6.2: Arrhenius Concept
- The Arrhenius acid-base concept defines acids and bases in terms of how they affect the amount of hydronium ions (and by extension hydroxide ions in aqueous solutions. Simply, in the Arrhenius definition an acid is a substance that increases the concentration of hydronium ions when it is dissolved in water. This typically occurs when the acid dissociates by loss of a proton to water.
- 6.3: Brønsted-Lowry Concept
- 6.3.1: Brønsted-Lowry Concept
- 6.3.2: Rules of Thumb for thinking about the relationship between Molecular Structure and Brønsted Acidity and Basicity*
- 6.3.3: The acid-base behavior of binary element hydrides is determined primarily by the element's electronegativity and secondarily by the element-hydrogen bond strength.*
- 6.3.4: Brønsted-Lowry Superacids and the Hammett Acidity Function
- 6.3.5: Thermodynamics of Solution-Phase Brønsted Acidity and Basicity
- 6.3.6: Thermodynamics of Gas Phase Brønsted Acidity and Basicity
- 6.3.7: The Acidity of an Oxoacid is Determined by the Electronegativity and Oxidation State of the Oxoacid's Central Atom*
- 6.3.8: High Charge-to-Size Ratio Metal Ions Act as Brønsted Acids in Water
- 6.3.9: The Solvent System Acid Base Concept
- 6.3.10: Acid-Base Chemistry in Amphoteric Solvents and the Solvent Leveling Effect
- 6.3.11: Non-nucleophilic Brønsted-Lowry Superbases
- 6.4: Lewis Concept and Frontier Orbitals
- 6.4.1: 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.
- 6.4.2: 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
- 6.4.3: The electronic spectra of charge transfer complexes illustrate the impact of frontier orbital interactions on the electronic structure of Lewis acid-base adducts
- 6.4.4: 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.
- 6.4.5: In the boron trifluoride affinity scale, the enthalphy change on formation of an adduct between the base and boron trifluoride is taken as a measure of Lewis basicity.
- 6.4.6: Lewis base strength may also be estimated by measuring structural or energy changes upon formation of a Lewis acid-base complex, as illustrated by efforts to spectroscopically assess the strengths of halogen bonds
- 6.4.7: Bulky groups weaken the strength of Lewis acids and bases because they introduce steric strain into the resulting acid-base adduct.
- 6.4.8: Frustrated Lewis pair chemistry uses Lewis acid and base sites within a molecule that are sterically restricted from forming an adduct with each other.
- 6.6: Hard and Soft Acids and Bases
- 6.6.1: Quantitative Measures of Hardness, Softness, and Acid-Base Interactions from a Hard Soft Acid-Base Principle Perspective Involve Orbital Energies and/or Apportioning Acid-Base Bonding in Terms of Electrostatic and Covalent Factors
- 6.6.2: Hard-Hard and Soft-Soft preferences may be explained and quantified in terms of electrostatic and covalent and electronic stabilization on the stability of Lewis acid-base adducts