Acid-Base Concepts

Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

Acid-Base Concepts
The definitions of an acid and a base range from proton and hydroxide donors to electron pair donors and acceptors to specialized definitions for non-solvent systems.

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Acid-Base Definitions
Arrhenius - Acids are proton donors, bases are hydroxide donors.

Bronsted-Lowry - Acids are proton donors, bases are proton acceptors.

Lux-Flood - Acids are oxide acceptors, bases are oxide donors.

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Acids are oxide acceptors, bases are oxide donors

Lux-Flood Reactions

CaO + SiO2 CaSiO3

base acid

CaO + H2O Ca2+ + 2 OHbasic anhydride

SiO2 + H2O H2SiO3

acidic anhydride
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Acid-Base Definitions Dont Have To Be Limited to H & O

(CH3)4N+ ClFeCl3 bases are chloride donors acids are chloride acceptors

(CH3)4N+ Cl- + FeCl3 OPCl3 or OP(OEt)3

(CH3)4N+ + FeCl4-

Solvent Systems
Autoionization

2 H2O 2 NH3 2 OPCl3

H3O+ + OHNH4+ + NH2OPCl2+ + OPCl4-

strongest acid allowed in solvent

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strongest base allowed in solvent

Solvent Systems
Acid Leveling
acids stronger than H3O+ are leveled to H3O+ bases stronger than OHare leveled to OH-

2 H2O

H3O+ + OH-

HNO3 + H2O H3O+ + NO3CaO + H2O Ca2+ + 2 OH3/22/2012

Solvent Systems
Acid Leveling
What is the strongest acid and the strongest base allowed in liquid hydrofluoric acid? 3 HF H2F+ + HF2-

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Other Acid-Base Definitions

Lewis - Acids are electron pair acceptor, bases are electron pair donors.

Usanovich - Acids are negative charge acceptors, bases are negative charge donors.

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General Acid-Base Concepts

metalloids are amphoteric nonmetal oxides are acidic

metal oxides are basic

more basic

General Acid-Base Concepts

Beryllium oxide is amphoteric high charge density causes polarization of any electron source BeO is more acidic and less basic than other alkaline earth oxides. BeO + 2 H+ BeO + H2O + 2 OHBe2+ + H2O Be(OH)42-

General Acid-Base Concepts

Hydration and Hydrolysis coordination of the solvent (solvation) releases energy and stabilizes the product high charge density ions have large hydration (solvation) energies Na+ + n H2O [Na(H2O)n]+

General Acid-Base Concepts

Hydration and Hydrolysis If the cation is acidic enough, it can polarize the oxygen of water away from the hydrogen. Al3+ + 6 H2O
the pH of 0.1 M Al(NO3)3 is 3.07

[Al(H2O)6]3+
H2O

[Al(H2O)5 (OH)]2+ + H3O+

Why is 0.1 M iron(III) ion even more acidic?

General Acid-Base Concepts

Oxyacids

HmXOn

The acidity of oxyacids depends on formal charge on the central atom charge on the complex inductive effects of substituents

General Acid-Base Concepts

Oxyacids HmXOn if n-m 2, strong acid pKa << 0 = 1, weak acid pKa 2.1 0.9 = 0, very weak acid pKa 8.5 1 sequential proton loss leads to pK2 values of +5 greater
Examples: HNO3 HNO2 HSO4HClO3 H3PO4 H2PO4-

HClO2

HClO

HNO3
HNO2 HSO4HClO2

<< 0
3.3 1.9 HClO2

HClO3 H3PO4 HClO

HClO3 2.1 7.5

H2PO4- 7.2

General Acid-Base Concepts

Oxyacids

HmXOn

The acidity of oxyacids depends on formal charge on the central atom charge on the complex inductive effects of substituents

pKa = 10.5 - 5.0 n - x

for X(OH)mOn

General Acid-Base Concepts

Oxyacids Special Cases

H2SO3
H3PO3 H2CO3

pKa = 1.81
pKa = 2.00 pKa = 6.37

H3BO3

pKa = 9.1

General Acid-Base Concepts

Substituted Amines

NR3

The basicity of amines depends on inductive effects of substituents steric effects

pKb NF3
no basic character

NH3
4.74

NH2CH3
3.36

NH(CH3)2
3.29

N(CH3)3
4.28

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