The Bronsted Definition of Acids and Bases

A powerful definition of acids and bases was proposed in 1923 by J.N. Bronsted [9], namely an acid is a species capable of donating a proton, and a base is a species capable of accepting a proton. This can be expressed by the scheme 

The only reactions between Bronsted acids and Bronsted bases that can be observed in solution and studied directly in the gas phase are reactions of proton exchange between two conjugate acid/base pairs A /B and A /B  

For example, in aqueous solutions, the acid CH3COOH reacts with water acting as a base CH3COOH + H2O H3O+ -I- CH3C00 (1.3) 

Inorganic oxyacids HNO3, H2SO4, H3PO4, HCIO4 

Phenols, alcohols, water ArOH, ROH, H2O N-H acids ArNH2, RSO2NH2, RCONH2, HNCS, HNCO, HN3 

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The Bronsted definitions of acids and bases are more general than the Arrhenius definitions they also apply to species in nonaqueous solvents and even to gas-phase reactions. For example, when pure acetic acid is added to liquid ammonia, proton transfer takes place and the following equilibrium is reached ... 

An important implication of the Bronsted definitions of acids and bases is that the same substance may be able to function as both an acid and a base. For example, we have seen that a water molecule accepts a proton from an acid molecule (such as HC1 or HCN) to form an H30+ ion. So water is a base. I lowever, a water molecule can donate a proton to a base (such as O2- or NH3) and become an OH ion. So water is also an acid. We describe water as amphiprotic, meaning that an H20 molecule can act both as a proton donor and as a proton acceptor. 

The nature of catalysis in homogeneous systems has been the subject of a considerable amount of research. A catalyst is any substance which affects the rate of reaction but is not consumed in the overall reaction. From thermodynamic principles we know that the equilibrium constant for the overall reaction must be independent of the mechanism, so that a catalyst for the forward reaction must also be one for the reverse reaction. In aqueous solution, a large number of reactions are catalyzed by acids and bases for our purposes we shall employ the Bronsted definition of acids and bases as proton donors and acceptors, respectively. Catalysis by acids and bases involves proton transfer either to or from the substrate. For example, the dehydration of acetaldehyde hydrate is subject to acid catalysis [20], probably by the mechanism (II). 

An extension of the Bronsted definition of acids and bases is the concept of the conjugate add-base pair, which can be defined as an acid and its conjugate base or a base and its conjugate acid. The conjugate base of a Bronsted acid is the species that remains when one proton has been removed from the acid. Conversely, a conjugate acid results from the addition of a proton to a Bronsted base. 

The Bronsted definitions of acids and bases are not restricted to species in aqueous solution. In fact, Bronsted acid-base reactions sometimes take place in the gas phase. For example, in the reaction between HCl and NH3 gases, HCl acts as the Bronsted acid, donating its proton to NH3, which, by accepting the proton, acts as a Bronsted base. The products of this proton transfer are the chloride ion (Cl ) and the armnonium ion (NH4), which subsequently combine to form the ionic solid ammoninm chloride. 

The Lewis definition of acids and bases is broader and more encompassing than the Bronsted-Lowry definition because it s not limited to substances that donate or accept just protons. A Lewis acid is a substance that accepts an electron pair, and a Lewis base is a substance that donates an electron pair. The donated electron pair is shared between the acid and the base in a covalent bond. 

Any text on acids and bases would not be deemed complete if mention were not made of the extended definition of acids and bases that is embodied in the Lowry-Bronsted theory. The theory basically proposed a more general definition of acids and bases to overpower the limitations of the theory arising from the Arrhenius concept. 

Lewis defined a base as an electron pair donor and an acid as an electron pair acceptor. Lewis electron pair donor was the same as Bronsted-Lowry s proton acceptor, and therefore, was an equivalent way of defining a base. Lewis acids were defined as a substance with an empty valence shell that could accommodate a pair of electrons. This definition broadened the Bronsted-Lowry definition of an acid. The three definitions of acids and bases are summarized in Table 13.3. 

You no doubt noticed that some of the bases in Table 16-1 don t contain a hydroxide ion, which means that the Arrhenius definition of acids and bases can t apply. When chemists realized that several substances behaved like bases but didn t contain a hydroxide ion, they reluctantly acknowledged that another determination method was needed. Independently proposed by Johannes Bronsted and Thomas Lowry in 1923 and therefore named cifter both of them, the Bronsted-Lowry method for determining acids and bases accounts for those pesky non-hydroxide-containing bases. 

Before continuing on to the last definition of acids and bases, it will be helpful to consider the definitions for strong and weak acids within the context of the Bronsted-Lowry model of acids and bases. The definitions are really an extension of the Arrhenius ideas. In the Arrhenius definitions, strong acids and bases were those that ionize completely. Most Bronsted-Lowry acids and bases do not completely ionize in solution, so the strengths are determined based on the degree of ionization in solution. For example, acetic acid, found in vinegar, is a weak acid that is only about 1 percent ionized in solution. That means that when acetic acid, HC2H302, is placed in water, the reaction looks like ... 

The Lewis definition of acids and bases also encompasses the Bronsted-Lowry definition. For example,... 

Compare the Bronsted-Lowry definitions of acids and bases with the Arrhenius definitions of acids and bases. 

THE BRONSTED definition OF ACIDITY AND BASICITY. PROPERTIES OF ACIDS AND BASES... 

Because both dihydrogen phosphate and hydrogen carbonate (and other substances like them) can be either Bronsted-Lowry acids or bases, they cannot be described as a Bronsted-Lowry acid or base except with reference to a specific acid-base reaction. For this reason, the Arrhenius definitions of acids and bases are the ones used to categorize isolated substances on the stockroom shelf A substance generates either hydronium ions, hydroxide ions, or neither when added to water, so it is always either an acid, a base, or neutral in the Arrhenius sense. Hydrogen carbonate is an Arrhenius base because it yields hydroxide ions when added to water. Dihydrogen phosphate is an Arrhenius acid because it generates hydronium ions when added to water. 

One of the earliest definitions of acids and bases is the Arrhenius theory. According to this theory, an acid dissociates to form hydrogen ions, H+, and a base dissociates to form hydroxide ions, OH . The Bronsted-Lowry theory defines an acid as a proton (H+) donor and a base as a proton acceptor. 

Ammonia—a Bronsted-Lowry base All of the acids and bases that fit the Arrhenius definition of acids and bases also fit the Bronsted-Lowry definition. But some other substances that lack a hydroxide group and, therefore, cannot be considered bases according to the Arrhenius definition can be classified as acids according to the Bronsted-Lowry model. One example is ammonia (NHsj.When ammonia dissolves in water, water is a Bronsted-Lowry acid in the forward reaction. Because the NH3 molecule accepts a H+ ion to form the ammonium ion (NH4+), ammonia is a Bronsted-Lowry base in the forward reaction. 

Our emphasis throughout this chapter has been on water as the solvent and on the proton as the source of acidic properties. In such cases we find the Bronsted—Lowry definition of acids and bases to be the most useful. In fact, when we speak of a substance as being acidic or basic, we are usually thinking of aqueous solutions and using these terms in the Arrhenius or Bronsted—Lowry sense. The advantage of the Lewis definitions of acid and base is that they allow us to treat a wider variety of reactions, including those that do not involve proton transfer, as acid—base reactions. To avoid confusion, a substance such as BF3 is rarely called an acid unless it is clear from the context that we are using the term in the sense of the Lewis definition. Instead, substances that function as electron-pair acceptors are referred to explicitly as Lewis acids. ... 

You have reviewed the Bronsted-Lowry definition of acids and bases and the meanings of pH and pTQ. You have learned to identify the most acidic hydrogen atoms in a molecule based on a comparison of pIQ values. You will see in many cases that Brensted—Lowry acid-base reactions either initiate or complete an organic reaction, or prepare an organic molecule for further reaction. The Lewis definition of acids and bases may have been new to you. However, you will see over and over again that Lewis acid—base reactions which involve either the donation of an electron pair to form a new covalent bond or the departure of an electron pair to break a covalent bond are central steps in many organic reactions. The vast majority of organic reactions you will study are either Bronsted-Lowry or Lewis acid—base reactions. 

Apart from this modification, the Arrhenius definitions of acid and base are still valid and useful today, as long as we are talking about aqueous solutions. However, the Arrhenius concept of acids and bases is so intimately tied to reactions that take place in water that it has no good way to deal with acid-base reactions in nonaqueous solutions. For this reason, we concentrate in this chapter on the Bronsted-Lowry definitions of acids and bases, which are more useful to us in our discussion of reactions of organic compounds. 

Finally, we learn the Lewis definitions of acid and base. A Lewis acid is an electron acceptor, and a Lewis base is an electron donor. The Lewis definitions are more general and inclusive than either Arrhenius or Bronsted-Lowry. 

Although the Arrhenius definition of acids and bases works in many cases, it cannot easily explain why some substances act as bases even though they do not contain OH . The Arrhenius definition also does not apply to nonaqueous solvents. A second definition of acids and bases, called the Bronsted-Lowry definition, introduced in 1923, applies to a wider range of acid-base phenomena. This definition focuses on the transfer of H ions in an acid-base reaction. Since an H ion is a proton—a hydrogen atom with its electron taken away—this definition focuses on the idea of a proton donor and a proton acceptor. 

The Lewis definition of acids and bases is broader than the Bronsted-Lowry definition. According to the Lewis definition, acidity and basicity are described in terms of electrons, rather than protons. A Lewis acid is defined as an electron acceptor, while a Lewis base is defined as an electron donor. As an illustration, consider the following Bronsted-Lowry acid-base reaction ... 

In Section 1.7 (p. 41), we introduced acids and bases. Now we know quite a bit more about structure and can return to the important subject of acids and bases in greater depth. In particular, we know about carbocations and carbanions, which play an important role in acid—base chemistry in organic chemistry The Lewis definition of acids and bases is far more inclusive than the Bronsted definition, which focuses solely on proton donation (Breasted acid) and acceptance (Breasted base). The archetypal Brensted acid-base reaction is the reaction between KOH and HCl to transfer a proton from HCl to HO. This reaction is a competition between the hydroxide and the chloride for a proton. In this case, the stronger base hydroxide wins easily (Rg. 2.57). 

Although the Bronsted concept of acids and bases focuses on the transfer of a proton, electron pairs are more fundamental to the process. Covalent bonds are formed or broken when a proton is transferred from one atom to another. To account for this possibihty, Gilbert N. Lewis proposed a definition of acids that focuses on electron pairs. A Lewis acid is an electron pair acceptor a Lewis base is an electron pair donor. This is a general definition of an acid and a base. For example, hydrochloric acid, a Bronsted acid, is also a Lewis acid because it contains a proton that accepts an electron pair. Ammonia is a Lewis base because it can act as an electron pair donor. However, many other species can serve as electron pair acceptors or donors. Consider the following general reaction between a Lewis acid and a Lewis base. 

A useful definition of acids and bases is that independently introduced by Johannes Bronsted (1879-1947) and Thomas Lowry (1874-1936) in 1923. In the Bronsted-Lowry definition, acids are proton donors, and bases are proton acceptors. Note that these definitions are interrelated. Defining a base as a proton acceptor means an acid must be available to provide the proton. For example, in reaction 6.7 acetic acid, CH3COOH, donates a proton to ammonia, NH3, which serves as the base. 

The problem with the Arrhenius definitions is that they are specific to one particular solvent, water. When chemists studied nonaqueous solvents, such as liquid ammonia, they found that a number of substances showed the same pattern of acid-base behavior, but plainly the Arrhenius definitions could not be used. A major advance in our understanding of what it means to be an acid or a base came in 1923, when two chemists working independently, Thomas Lowry in England and Johannes Bronsted in Denmark, came up with the same idea. Their insight was to realize that the key process responsible for the properties of acids and bases was the transfer of a proton (a hydrogen ion) from one substance to another. The Bronsted-Lowry definition of acids and bases is as follows ... 

Bronsted-Lowry definition A definition of acids and bases in terms of the ability of molecules and ions to participate in proton transfer. 

Any reaction in which a proton is transferred from one substance to another is an acid-base reaction. More specifically, the proton-transfer view is known as the Bronsted-Lowiy definition of acids and bases. In an acid-base reaction, an acid donates a proton, and a base accepts that proton. Any species that can give up a proton to another substance is an acid, and any substance that can accept a proton from another substance is a base. The production of two water molecules from a hydroxide anion (a base) and a hydronium ion (an acid) is just one example of an acid-base reaction acids and bases are abundant in chemistry. 

It was G. N. Lewis who extended the definitions of acids and bases still further, the underlying concept being derived from the electronic theory of valence. It provided a much broader definition of acids and bases than that provided by the Lowry-Bronsted concept, as it furnished explanations not in terms of ionic reactions but in terms of bond formation. According to this theory, an acid is any species that is capable of accepting a pair of electrons to establish a coordinate bond, whilst a base is any species capable of donating a pair of electrons to form such a coordinate bond. A Lewis acid is an electron pair acceptor, while a Lewis base is an electron pair donor. These definitions of acids and bases fit the Lowry-Bronsted and Arrhenius theories, and cover many other substances which could not be classified as acids or bases in terms of proton transfer. 

According to the Bronsted-Lowry definition of acids and bases, an acid is a proton donor. The particle that is left over after an acid donates its proton, however, can now accept a proton and,... 

The Br0nsted theory expands the definition of acids and bases to allow us to explain much more of solution chemistry. For example, the Brpnsted theory allows us to explain why a solution of ammonium chloride tests acidic and a solution of sodium acetate tests basic. Most of the substances that we consider acids in the Arrhenius theory are also acids in the Bronsted theory, and the same is true of bases. In both theories, strong acids are those that react completely with water to form ions. Weak acids ionize only slightly. We can now explain this partial ionization as an equilibrium reaction of the ions, the weak acid, and the water. A similar statement can be made about weak bases ... 

Thus, a reducing agent donates electrons, while an oxidizing agent receives them. The Bronsted-Lowry definitions of acid and base specify that... 

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