Acids and bases:

  • Acid dissociation constant
  • Acid-base extraction
  • Acid-base reaction
  • Dissociation constant
  • Acidity function
  • Buffer solutions
  • pH
  • Proton affinity
  • Self-ionization of water
  • Acids:
    • Lewis acids
    • Mineral acids
    • Organic acids
    • Strong acids
    • Superacids
    • Weak acids
  • Bases:
    • Lewis bases
    • Organic bases
    • Strong bases
    • Superbases
    • Non-nucleophilic bases
    • Weak bases
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An acid-base reaction is a chemical reaction that occurs between an acid and a base. Several concepts that provide alternative definitions for the reaction mechanisms involved and their application in solving related problems exist. Despite several differences in definitions, their importance becomes apparent as different methods of analysis when applied to acid-base reactions for gaseous or liquid species, or when acid or base character may be somewhat less apparent. The first of these scientific concepts of acids and bases was provided by the French chemist Antoine Lavoisier, circa 1776.

Common acid-base theories

Lavoisier definition

Since Lavoisier's knowledge of strong acids was mainly restricted to oxoacids, which tend to contain central atoms in high oxidation states surrounded by oxygen, such as HNO 3 and H 2 SO 4 , and since he was not aware of the true composition of the hydrohalic acids (HF, HCl, HBr, and HI), he defined acids in terms of their containing oxygen , which in fact he named from Greek words meaning "acid-former" (from the Greek οξυς ( oxys ) meaning "acid" or "sharp" and γεινομαι ( geinomai ) meaning "engender"). The Lavoisier definition was held as absolute truth for over 30 years, until the 1810 article and subsequent lectures by Sir Humphry Davy in which he proved the lack of oxygen in H 2 S, H 2 Te, and the hydrohalic acids.

Liebig definition

This definition is proposed by Justus von Liebig circa 1838, based on his extensive works on the chemical composition of organic acids. This finished the doctrinal shift from oxygen-based acids to hydrogen-based acids, started by Davy. According to Liebig, an acid is a hydrogen-containing substance in which the hydrogen could be replaced by a metal. Liebig's definition, while completely empirical, remained in use for almost 50 years until the adoption of the Arrhenius definition.

Arrhenius definition

The Arrhenius definition of acid-base reactions is a more simplified acid-base concept devised by Svante Arrhenius, which was used to provide a modern definition of bases that followed from his work with Friedrich Wilhelm Ostwald in establishing the presence of ions in aqueous solution in 1884, and led to Arrhenius receiving the Nobel Prize in Chemistry in 1903 for "recognition of the extraordinary services... rendered to the advancement of chemistry by his electrolytic theory of dissociation".

As defined at the time of discovery, acid-base reactions are characterized by Arrhenius acids, which dissociate in aqueous solution form hydrogen ions (H + ) later recognized to be actually hydronium (H 3 O + ) ions, and Arrhenius bases which form hydroxide (OH ) ions. More recent IUPAC recommendations now suggest the newer term "hydronium" be used in favor of the older accepted term "oxonium" to illustrate reaction mechanisms such as those defined in the Brønsted-Lowry and solvent system definitions more clearly, with the Arrhenius definition serving as a simple general outline of acid-base character. The Arrhenius definition can be summarised as "Arrhenius acids form hydrogen ions in aqueous solution with Arrhenius bases forming hydroxide ions."

The universal aqueous acid-base definition of the Arrhenius concept is described as the formation of water from hydrogen and hydroxide ions, or hydrogen ions and hydroxide ions from the dissociation of an acid and base in aqueous solution:

(In modern times, the use of H + is regarded as a shorthand for H 3 O + , since it is now known that the bare proton H + does not exist as a free species in solution.)

This leads to the definition that in Arrhenius acid-base reactions, a salt and water is formed from the reaction between an acid and a base. In other words, this is a neutralization reaction.

The positive ion from a base forms a salt with the negative ion from an acid. For example, two moles of the base sodium hydroxide (NaOH) can combine with one mole of sulfuric acid (H 2 SO 4 ) to form two moles of water and one mole of sodium sulfate.

Brønsted-Lowry definition

Main article: Brønsted–Lowry acid-base theory

The Brønsted-Lowry definition, formulated independently by its two proponents Johannes Nicolaus Brønsted and Martin Lowry in 1923, is based upon the idea of protonation of bases through the de-protonation of acids—that is, the ability of acids to "donate" hydrogen ions (H + ) or protons to bases, which "accept" them. Unlike the Arrhenius definition, the Brønsted-Lowry definition does not refer to the formation of salt and water, but instead to the formation of conjugate acids and conjugate bases , produced by the transfer of a proton from the acid to the base.

In this definition, an acid is a compound that can donate a proton, and a base is a compound that can receive a proton. An acid-base reaction is, thus, the removal of a hydrogen ion from the acid and its addition to the base. This does not refer to the removal of a proton from the nucleus of an atom, which would require levels of energy not attainable through the simple dissociation of acids, but to removal of a hydrogen ion (H + ).

The removal of a proton (hydrogen ion) from an acid produces its conjugate base , which is the acid with a hydrogen ion removed, and the reception of a proton by a base produces its conjugate acid , which is the base with a hydrogen ion added.

For example, the removal of H + from hydrochloric acid (HCl) produces the chloride ion (Cl ), the conjugate base of the acid:

The addition of H + to the hydroxide ion (OH ), a base, produces water ( H 2 O ), its conjugate acid:

Thus, the Brønsted-Lowry definition encompasses the Arrhenius definition, but also extends the concept of acid-base reactions to systems in which water is not involved, such as the protonation of ammonia, a base, to form the ammonium ion, its conjugate acid:

This reaction may proceed in the absence of water, such as in the reaction of ammonia with acetic acid:

This definition also provides a theoretical framework for explaining the spontaneous dissociation of water into low concentrations of hydronium and hydroxide ions:

Water, being amphoteric, can act as both an acid and a base; here, one molecule of water acts as an acid, donating a H + ion and forming the conjugate base, OH , and a second molecule of water act as a base, accepting the H + ion and forming the conjugate acid, H 3 O + .

Bronsted-lowry-3d-explanation-diagram.png

Thus, the general formula for acid-base reactions according to the Brønsted-Lowry definition is:

where AH represents the acid, B represents the base, and BH + represents the conjugate acid of B, and A represents the conjugate base of AH.

Lewis definition

Further information: Lewis acids and bases

The Lewis definition of acid-base reactions, devised by Gilbert N. Lewis in 1923 is a further generalization that encompasses the Brønsted-Lowry definition and the solvent-system definitions. Instead of defining acid-base reactions in terms of protons or other bonded substances, the Lewis definition defines a base (referred to as a Lewis base ) to be a compound that can donate an electron pair , and an acid (a Lewis acid ) to be compound that can receive this electron pair.

For example, consider this classical aqueous acid-base reaction:

The Lewis definition does not regard this reaction as the formation of salt and water or the transfer of H + from HCl to OH . Instead, it regards the acid to be the H + ion itself, and the base to be the OH ion, which has an unshared electron pair. Therefore, the acid-base reaction here, according to the Lewis definition, is the donation of the electron pair from OH to the H + ion. This forms a covalent bond between H + and OH , thus producing water ( H 2 O ).

By treating acid-base reactions in terms of electron pairs instead of specific substances, the Lewis definition can be applied to reactions that do not fall under other definitions of acid-base reactions. For example, a silver cation behaves as an acid with respect to ammonia, which behaves as a base, in the following reaction:

The result of this reaction is the formation of an ammon

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