The Lewis and Brønsted Theories of Acidity
The chemogenesis analysis uses the concept of Lewis acids and Lewis bases extensively, and the Brønsted model of acidity is employed as well. It is essential that the reader is quite clear about the similarities and differences between the two approaches. This page reviews these issues.

Introduction

In the Lowry-Brønsted model: "a [Brønsted] acid is a proton donor".

In the Lewis model: "a [Lewis] acid is an electron-pair acceptor".

The two theories can be reconciled by recognising that the proton, H+, is a unique and versatile Lewis acid that is the agent of Brønsted acidity.

The Lewis model is more general than the more common Brønsted model.

Some statements:

  • All Brønsted acids are proton/Lewis base complexes.

  • The transfer of H+ between Lewis bases equates with Brønsted acidity.

  • While a Brønsted acid is an H+ donor, the proton, H+, is a Lewis acid.

  • All Lewis bases can be protonated. It follows that the ability of a species to complex a proton defines that species as being both a Brønsted base and a Lewis base.

  • Any species able to complex with a Lewis base is a Lewis acid.
A Model Reaction

Consider hydrogen chloride reacting with water:

HCl       +       :OH2             [H3O]+       +        Cl–

The Brønsted description of this reaction says:

  • Hydrogen chloride, HCl, is the proton donor [Brønsted] acid and water, :OH2, is the proton-accepting [Brønsted] base.

  • The oxonium ion, [H3O]+, is the conjugate [Brønsted] acid and the chloride ion, Cl–, is the conjugate [Brønsted] base.

The Lewis description of this reaction says:

  • The chloride ion, Cl–, and water, :OH2, are both Lewis bases and they compete with each other to complex the proton Lewis acid, H+.

  • The water Lewis base "wins" and the proton transfers from chloride ion to water. Thus, hydrogen chloride is an H+/Cl– complex that transfers H+ to water to give the oxonium ion, [H3O]+.

  • The oxonium ion is an H+/water complex, H+/:OH2.

In the Brønsted analysis, all proton acceptors (Brønsted bases) are standardised against the aqueous Brønsted base, water, :OH2. The measure is expressed as the reaction equilibrium constant, Ka or pKa. Therefore,

  • The term Brønsted base refers to proton affinity with respect to water, H2O:

  • pH is a measure of hydrogen ion concentration in water. For good reasons, see here, pH is defined as "minus the log10 of the hydrogen ion concentration":

pH = –log10[H+]

  • The term Lewis base is more general and refers to the propensity to complex with a Lewis acid. Lewis bases can present as nucleophiles, ligands, spectator anions or electron rich p-systems, as well as proton abstractors. There is no general scale of Lewis acid or Lewis base behaviour, although periodicity can be observed as discussed in this webbook.

Due to the potential for confusion, throughout the chemogenesis web book the word "acid" is always proceeded by the qualifier "Lewis" or "Brønsted".

Nucleophiles & Bases
HSAB Principle

© Mark R. Leach 1999-2008

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