Lewis acid—base theory

In 1923, the same year that Bransted and Lowry came up with their idea of what acids and bases were, an American chemist named Gilbert Newton Lewis began to work on his own acid-base theory. Lewis defined acid as any substance that accepted an electron pair. A base, on the other hand, is any substance that donates an electron pair. 

The binding of a metal ion to a ligand can be considered in terms of Lewis acid-base theory (Lewis, 1923 Allred and Rochow, 1958 Brown and Skowron, 1990) because, in accepting an electronic pair, the metal ion acts as a Lewis acid. When a metal ion coordinates a ligand, it can affect the electron distribution of the ligand and therefore its reactivity. 

At about the same time that Bronsted proposed his acid-base theory, Lewis put forth a broader theory, A base in the Lewis theory is the same as in the Brpnsted one, namely, a compound with an available pair of electrons, either unshared or in a tt orbital. A Lewis acid, however, is any species with a vacant orbital.1115 In a Lewis acid-base reaction the unshared pair of the base forms a covalent bond with the vacant orbital of the acid, as represented by the general equation... 

Two acid-base theories are used in organic chemistry today the Br0nsted theory and the Lewis theory. These theories are quite compatible and are used for different purposes. ... 

At about the same time that Brpnsted proposed his acid-base theoiy, Lewis put forth a broader theory. A base in the Lewis theory is the same as in the Brpnsted one. 

For a monograph on Lewis acid-base theory, see Jensen, W.B. The Lewis Acid-Base Concept Wiley NY, 1980. For a discussion of the definitions of Lewis acid and base, see Jensen, W.B. Chem. Rev, 1978, 78, 1. 

From this discussion it can be seen that there is no ideal acid-base theory for AB cements and a pragmatic approach has to be adopted. Since the matrix is a salt, an AB cement can be defined quite simply as the product of the reaction of a powder and liquid component to yield a salt-like gel. The Bronsted-Lowry theory suffices to define all the bases and the protonic acids, and the Lewis theory to define the aprotic acids. The subject of acid-base balance in aluminosilicate glasses is covered by the Lux-Flood theory. 

From our previous treatment of the Arrhenius, Bransted and Lewis acid-base theories, the importance of the choice between the divergent solvent types clearly appeared if we now confine ourselves to solvents to which the proton theory in general is applicable, this leads to a classification of eight classes as already proposed by Bronsted35,36 (Table 4.3). 

B The Lewis Definition of Acids and Bases 1. Lewis acid-base theory in 1923 proposed by G. N. Lewis (1875-1946 Ph. D. Harvard, 1899 professor, Massachusetts Institute of Technology, 1905-1912 professor, University of California, Berkeley, 1912-1946). 

Acid-base behavior according to the Lewis theory has many of the same aspects as does acid-base theory according to the Bronsted-Lowry theory. 

Besides chemical bonds, Lewis also studied thermodynamics, isotopes and light. He expanded his theories of chemical bonding and also proposed the Lewis acid-base theory. 

Another acid-base theory is the Lewis acid-base theory. According to this theory, a Lewis acid will accept a pair of electrons and a Lewis base will donate a pair of electrons. In order to make it easier to see which species is donating electrons, it is helpful to use Lewis structures for the reactants and if possible for the products. 

Discuss the binding of metal ions and of ligands in terms of the Lewis-acid-base theory. 

Klopman has applied HOMO-LUMO arguments to hard-soft Lewis acid—base theory.10 Although his treatment is a quantitative one, we shall describe only its... 

Students should review / V / Lewis acid-base theory in... 

Chlorhexidine is a strong base (Lewis acid-base theory) because it reacts with acids to form salts of the RX2 type, and it is practically insoluble in water (<0.008% wt/vol at 20°C). The water solubility of the different salts varies widely as demonstrated in Table 2.13. Chlorhexidine is moderately surface-active (a net+chare over its surface) and forms micelles (molecular aggregates form colloidal particles) in solution the critical micellar concentration of the acetate is 0.01% wt/vol at 25°C (Heard and Ashworth 1969). Aqueous solutions of chlorhexidine are most stable within the pH range of 5-8, and above pH 8.0 chlorhexidine is precipitated because conditions for a base (>pH 7) reaction are present. 

The Lewis acid-base theory doesn t affect the category of compounds we have called bases because any Bnynsted base must have a pair of nonbonding electrons in order to accept a proton. This theory, however, vastly expanded the family of compounds that can be called acids. Anything that has one or more empty valence-shell orbitals can now act as an acid... 

In combustion analysis of organic compounds, solid NaOH is used to absorb the CO2 from the combustion gases. Account for this reaction in terms of Lewis acid-base theory. 

Considerable progress in the development of theoretical and synthetic coordination and organometallic chemistry was made with the use of electron ideas. Lewis elaborated in 1923 the classic electron theory of acids and bases [30], and used it to explain the coordination ideas of Werner [31] (in Ref. 32, this achievement is ascribed to Sidgwick). A Lewis acid (A) is a acceptor of the electron pair and a Lewis base (B) is its donor [33], In other words, A is a species that can form a new covalent bond by accepting a pair of electrons and B is a species that can form a new covalent bond by donating a pair of electrons. The fundamental Lewis acid-base theory is described by a direct equlibrium [Scheme (1.1)], leading to the formation of the adduct (acid-base complex) ... 

The topic of interactions between Lewis acids and bases could benefit from systematic ab initio quantum chemical calculations of gas phase (two molecule) studies, for which there is a substantial body of experimental data available for comparison. Similar computations could be carried out in the presence of a dielectric medium. In addition, assemblages of molecules, for example a test acid in the presence of many solvent molecules, could be carried out with semiempirical quantum mechanics using, for example, a commercial package. This type of neutral molecule interaction study could then be enlarged in scope to determine the effects of ion-molecule interactions by way of quantum mechanical computations in a dielectric medium in solutions of low ionic strength. This approach could bring considerable order and a more convincing picture of Lewis acid base theory than the mixed spectroscopic (molecular) parameters in interactive media and the purely macroscopic (thermodynamic and kinetic) parameters in different and varied media or perturbation theory applied to the semiempirical molecular orbital or valence bond approach [11 and references therein]. 

Acceptor number (or acceptivity), AN — is an empirical quantity for characterizing the electrophilic properties (-> Lewis acid-base theory) of a solvent A that expresses the solvent ability to accepting an electron pair of a donor atom from a solute molecule. AN is defined as the limiting value of the NMR shift, S, of the 31P atom in triethylphosphine oxide, Et3P=0, at infinite dilution in the solvent, relative to n-hexane, corrected for the diamagnetic susceptibility of the solvent, and normalized ... 

Lewis acid-base theory— To describe reactions where no proton transfer occurs, - Lewis has proposed a more general acid-base concept where an acid is a molecule or an ion with an incomplete outer electron sphere, i.e., an acceptor of electron pairs. A base is a molecule or an ion having a free electron pair, i.e., an electron pair donor. A neutralization reaction is characterized by the formation of a coordination or covalent bond. The following reactions illustrate the Lewis-definition ... 

Refs. [i] Finston H, Rychtman AC (1982) A new view of current acid-base theories. Wiley, New York [ii] Hand CW, BlewittHL (1986) Acid-base chemistry. Macmillan, New York [iii] )ensen WB (1980) The Lewis acid-base concepts. Wiley, New York [iv] Tanabe K (1989) New solid acids and bases. Elsevier, Amsterdam... 

Donor number (or donicity), DN — is an empirical semiquantitative measure of nucleophilic properties (-> acid-base theories, subentry Lewis acid-base theory) of a solvent defined as the negative of the standard molar heat of reaction (expressed in kcalmol-1) of the solvent D with antimony pentachloride to give the 1 1 adduct, when both are in dilute solution in the inert diluent 1,2-dichloroethane, according to the reaction scheme ... 

Electrophilic reagents are Lewis acids (- acid-base theories). Electrophilic catalysis is catalysis by Lewis acids. The term electrophilic is also used to designate the apparent polar character of certain -> radicals, as inferred from their higher relative reactivities with reaction sites of higher -> electron density. See also -> electrophilicity. Ref. [i] Muller P (1994) Pure Appl Chem 66 1077... 

Electrophilicity — (1) The property of being - electrophilic (see -> electrophile). (2) The relative reactivity of an electrophilic reagent. (It is also sometimes referred to as electrophilic power ) Qualitatively, the concept is related to Lewis acidity (- acid-base theories). However, whereas Lewis acidity is measured by relative - equilibrium constants, electrophilicity is measured by relative -> rate constants for reactions of different electrophilic... 

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