Download - Acid-Base and Donor-Acceptor Chemistry
![Page 1: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/1.jpg)
Acid-Base and Donor-Acceptor Chemistry
Chapter 6
![Page 2: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/2.jpg)
Acids and BasesThe Major Acid-Base Definitions:
![Page 3: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/3.jpg)
Acids and Bases• Arrhenius:
Acid is proton source in water, base is hydroxide sourceAcid + Base = Salt + Water; HCl + NaOH NaCl + H2OWorks in aqueous solutions only
• Brønsted-Lowry:Acid is proton donor, base is proton acceptorAcid(1) + Base(1) Acid(2) + Base(2) Can this happen without water?
• Conjugate acid-base pairsReaction favors the weaker acid/base pairNon-aqueous solvents, gas and solid phase reactions
![Page 4: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/4.jpg)
Acids and Bases• Solvent system definition:
If a species can autoionize (autodissociate, form a cation and an anion), the cation is an acid and the anion is a base
• In this system, an acid increases [cation] and a base increases [anion]
Water: 2 H2O H3O+ + OH–
• HCl is an acid in this solvent system (increases [cation])HCl + H2O H3O+ + Cl–
![Page 5: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/5.jpg)
Protic Acids and Bases
![Page 6: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/6.jpg)
• Kion is K for the autoionization of the pure solvent
Solvent Acid Base pKion
H2SO4 H3SO4+ HSO4
–3.4 at 10 ºCH2O H3O+ OH– 14NH3 NH4
+ NH2– 27
• Acetic acid is acid in water, but base in H2SO4
CH3CO2H + H2SO4 HSO4– + CH3CO2H2
+
• Urea is a base in water, but an acid in liquid NH3
(NH2)2CO + NH3 NH4+ + (NH2)(NH)CO–
Protic Acids and Bases
![Page 7: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/7.jpg)
Aprotic Acids and Bases
![Page 8: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/8.jpg)
• Aprotic solvent systems: BrF3, PCl5
2 NH3 NH4+ + NH2
-
2 BrF3 BrF2+ + BrF4
–
2 PCl5 PCl4+ + PCl6
–
In BrF3, SbF5 is an acid and KF is a baseSbF5 + BrF3 SbF6
– + BrF2+
KF + BrF3 K+ + BrF4–
In this definition, Acid + Base = Solvent
• BrF2+ + BrF4
– 2 BrF3Acid Base Solvent
• Broader definition - acid/base character is related to the solvent
Aprotic Acids and Bases
![Page 9: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/9.jpg)
Lewis Acid-Base TheoryFrontier Orbitals: HOMO and LUMO
![Page 10: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/10.jpg)
Lewis Acid vs. Lewis Base vs. Oxidation vs. Reduction
![Page 11: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/11.jpg)
Lewis Acid vs. Lewis Base vs. Oxidation vs. Reduction
![Page 12: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/12.jpg)
Lewis Acid vs. Lewis Base vs. Oxidation vs. Reduction
![Page 13: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/13.jpg)
Lewis Acid vs. Lewis Base vs. Oxidation vs. Reduction
![Page 14: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/14.jpg)
Measuring Lewis Acid-Base Interaction Strength via Electronic Spectra
![Page 15: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/15.jpg)
Hard and Soft Acids and BasesExamples: Ionic Compound Solubility
AgF(s) + H2O(l) Ag+(aq) + F-(aq) Ksp = 205
AgCl(s) + H2O(l) Ag+(aq) + Cl-(aq) Ksp = 1.8 x 10-10
AgBr(s) + H2O(l) Ag+(aq) + Br-(aq) Ksp = 5.2 x 10-13
AgI(s) + H2O(l) Ag+(aq) + I-(aq) Ksp = 8.3 x 10-17
Similarly, solubility: Hg2F2 > Hg2Cl2 > Hg2Br2 > Hg2I2
BUT, LiF < LiI MgF2 is less soluble than MgCl2
AlF3 is less soluble than AgCl3
![Page 16: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/16.jpg)
Hard and Soft Acids and BasesExamples: Complexation
![Page 17: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/17.jpg)
Hard and Soft Acids and BasesExamples: Thiocyanate Bonding to Metals
SCN- can bond through S or N
S-binding with M = large, polarizable metals like Hg2+, Au+, Pd2+
N-binding with M = smaller, less polarizable metals: Zn2+, Ni2+
![Page 18: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/18.jpg)
![Page 19: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/19.jpg)
Hard and Soft Acids and BasesDefinitions
Hard base: small, not polarizable
Soft base: large, highly polarizable
![Page 20: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/20.jpg)
Hard and Soft Acids and BasesDefinitions
Hard acid: small, not polarizable
Soft acid: large, highly polarizable
![Page 21: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/21.jpg)
![Page 22: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/22.jpg)
![Page 23: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/23.jpg)
![Page 24: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/24.jpg)
![Page 25: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/25.jpg)
![Page 26: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/26.jpg)
![Page 27: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/27.jpg)
Relate to oxoanions.
![Page 28: Acid-Base and Donor-Acceptor Chemistry](https://reader036.vdocuments.net/reader036/viewer/2022081419/56813d27550346895da6eb1d/html5/thumbnails/28.jpg)