Bases Arrhenius theory

A note on good practice The entities that are regarded as acids and bases are different in each theory. In the Lewis theory, the proton is an acid in the Bronsted theory, the species that supplies the proton is the acid. In both the Lewis and Bronsted theories, the species that accepts a proton is a base in the Arrhenius theory, the species that supplies the proton acceptor is the base (Fig. 10.61. 

The case of m = Q corresponds to classical Arrhenius theory m = 1/2 is derived from the collision theory of bimolecular gas-phase reactions and m = corresponds to activated complex or transition state theory. None of these theories is sufficiently well developed to predict reaction rates from first principles, and it is practically impossible to choose between them based on experimental measurements. The relatively small variation in rate constant due to the pre-exponential temperature dependence T is overwhelmed by the exponential dependence exp(—Tarf/T). For many reactions, a plot of In(fe) versus will be approximately linear, and the slope of this line can be used to calculate E. Plots of rt(k/T" ) versus 7 for the same reactions will also be approximately linear as well, which shows the futility of determining m by this approach. 

Since Arrhenius, definitions have extended the scope of what we mean by acids and bases. These theories include the proton transfer definition of Bronsted-Lowry (Bronsted, 1923 Lowry, 1923a,b), the solvent system concept (Day Selbin, 1969), the Lux-Flood theory for oxide melts, the electron pair donor and acceptor definition of Lewis (1923, 1938) and the broad theory of Usanovich (1939). These theories are described in more detail below. 

Thus, adds and bases do not react directly but as solvent cations and anions. Since emphasis is placed upon ionization interactions, inherent addity and basidty is neglected, as are interactions in the non-ionic state. The theory is a simple extension of the Arrhenius theory and suffers from... 

The acidic character of acids depends on the availability ofhydrogen ions in their solution. An acid X3 is said to be stronger than another acid X2 if, in equimolar solutions, X3 provides more hydrogen ions than does X2. This will be possible provided that the degree of dissociation of X3 is greater than that of X2. Based on the Arrhenius theory of electrolytic dissociation, solutions may be classified in the manner shown in Figure 6.1. If the ionization of an acid is almost complete in water, the acid is said to be a strong acid, but if the... 

Figure 6.1 Classification of solutions based on Arrhenius theory.

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. 

Arrhenius theory explained a lot about acids and bases, but it did not explain everything. Not all bases release hydroxide ions. In fact, one of the most commonly used bases—baking soda... 

The Arrhenius concept was of basic importance because it permitted quantitative treatment of a number of acid-base processes in aqueous solutions, i.e. the behaviour of acids, bases, their salts and mixtures of these substances in aqueous solutions. Nonetheless, when more experimental material was collected, particularly on reaction rates of acid-base catalysed processes, an increasing number of facts was found that was not clearly interpretable on the basis of the Arrhenius theory (e.g. in anhydrous acetone NH3 reacts with acids in the absence of OH- and without the formation of water). It gradually became clear that a more general theory was needed. Such a theory was developed in 1923 by J. N. Br0nsted and, independently, by T. M. Lowry. 

Thus far, we have used the Arrhenius theory of acids and bases (Secs. 6.4 and 7,3) in which acids are defined as hydrogen-containing compounds that react with bases. Bases are compounds containing OH" ions or that form OH- ions when they react with water. Bases react with acids to form salts and water. Metallic hydroxides and ammonia are the most familiar bases to us. 

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 ... 

Arrhenius theory theory of acids and bases in which acids are defined as hydrogen-containing compounds that react with bases. 

If solutions that contain other ionized acids and bases are mixed, the reaction is still one that occurs between the H30+(aq) and Oil (aq). Therefore, the neutralization reaction between an acid and a base is that shown in Eq. (9.5) according to the Arrhenius theory. 

According to the Arrhenius theory of acids and bases, the acidic species in water is the solvated proton (which we write as H30+). This shows that the acidic species is the cation characteristic of the solvent. In water, the basic species is the anion characteristic of the solvent, OH-. By extending the Arrhenius definitions of acid and base to liquid ammonia, it becomes apparent from Eq. (10.3) that the acidic species is NH4+ and the basic species is Nl I,. It is apparent that any substance that leads to an increase in the concentration of NH4+ is an acid in liquid ammonia. A substance that leads to an increase in concentration of NH2- is a base in liquid ammonia. For other solvents, autoionization (if it occurs) leads to different ions, but in each case presumed ionization leads to a cation and an anion. Generalization of the nature of the acidic and basic species leads to the idea that in a solvent, the cation characteristic of the solvent is the acidic species and the anion characteristic of the solvent is the basic species. This is known as the solvent concept. Neutralization can be considered as the reaction of the cation and anion from the solvent. For example, the cation and anion react to produce unionized solvent ... 

Base strength refers to the relative tendency to produce OH- ions in aqueous solution by (1) the dissociation of soluble metal hydroxides or (2) by ionization reactions with water using Arrhenius theory. A more general definition, applying Bronsted-Lowry theory, is that base strength is a measure of the relative tendency to accept a proton from any acid. 

At the microscopic level, the Arrhenius theory defines acids as substances which, when dissolved in water, yield the hydronium ion (H30+) or H+(aq). Bases are defined as substances which, when dissolved in water, yield the hydroxide ion (OH). Acids and bases may be strong (as in strong electrolytes), dissociating completely in water, or weak (as in weak electrolytes), partially dissociating in water. (We will see the more useful Brpnsted-Lowry definitions of acids and bases in Chapter 15.) Strong acids include ... 

FIGURE 3.6 Reaction rate constant of the CO + OH reaction as a function of the reciprocal temperature based on transition state (—) and Arrhenius (-) theories compared with experimental data (after Ref. [10]). 

According to the Arrhenius theory (1887), acids and bases are defined in terms of their structure and the ions produced when they dissolve in water. 

The Arrhenius theory explains acid-base reactions as a combination of H (aq) and OH (aq). It provides insight into the heat of neutralization for the reaction between a strong acid and a strong base. (Strong acids and bases dissociate completely into ions in solution.) For example, consider the following reaction. 

The limitations of the Arrhenius theory of acids and bases are overcome by a more general theory, called the Bronsted-Lowry theory. This theory was proposed independently, in 1923, by Johannes Br0nsted, a Danish chemist, and Thomas Lowry, an English chemist. It recognizes an acid-base reaction as a chemical equilibrium, having both a forward reaction and a reverse reaction that involve the transfer of a proton. The Bronsted-Lowry theory defines acids and bases as follows ... 

Note that the word proton refers to the nucleus of a hydrogen atom — an H ion that has been removed from the acid molecule. It does not refer to a proton removed from the nucleus of another atom, such as oxygen or sulfur, that may be present in the acid molecule. As mentioned previously, ions share electrons with any species (ion or molecule) that has a lone pair of electrons. In aqueous solution, the proton bonds with a water molecule to form the hydronium ion. Unlike the Arrhenius theory, however, the Brqnsted-Lowry theory is not restricted to aqueous solutions. For example, the lone pair of electrons on an ammonia molecule can bond with H+, and liquid ammonia can act as a base. 

Unlike the Arrhenius theory, the Bronsted-Lowry theory of acids and bases can explain the basic properties of ammonia when it dissolves in water. See Figure 8.4. 

Arrhenius theory (1887) the theory stating that acids and bases are defined in terms of their structure and the ions produced when they dissolve in water defines an acid as a substance that produces hydrogen ions in water and a base as a substance that produces hydroxide ions in water (8.1) asymmetrical alkene an alkene that has different groups on either side of the double bond (2.2) atom the basic unit of an element, which still retains the element s properties (Review)... 

Arrhenius subsequently expanded his theories to form one of the most widely used and straightforward definitions of acids and bases. Arrhenius said that acids are substances that form hydrogen (H+) ions when they dissociate in water, while bases cire substances that form hydroxide (OH ) ions when they dissociate in water. 

Thus far we ve been using the Arrhenius theory of acids and bases (Section 4.5). According to Arrhenius, acids are substances that dissociate in water to produce hydrogen ions (H + ), and bases are substances that dissociate in water to yield hydroxide ions (OH-). Thus, HC1 and H2SO4 are acids, and NaOH and Ba(OH)o are bases. 

The Arrhenius theory accounts for the properties of many common acids and bases, but it has important limitations. For one thing, the Arrhenius theory is restricted to aqueous solutions for another, it doesn t account for the basicity of substances like ammonia (NH3) that don t contain OH groups. In 1923, a more general theory of acids and bases was proposed independently by the Danish chemist Johannes Bronsted and the English chemist Thomas Lowry. According to the Bronsted-Lowry theory, an acid is any substance (molecule or ion) that can transfer a proton (H + ion) to another substance, and a base is any substance that can accept a proton. In short, acids are proton donors, bases are proton acceptors, and acid-base reactions are proton-transfer reactions ... 

Account for the acidic properties of nitrous acid (HN02) in terms of the Arrhenius theory and the Bronsted-Lowry theory, and identify the conjugate base of HNO2. 

According to the Arrhenius theory, acids (HA) are substances that dissociate in water to produce H + (aq). Bases (MOH) are substances that dissociate to yield OH aq). The more general Bransted-Lowry theory defines an acid as a proton donor, a base as a proton acceptor, and an acid-base reaction as a proton-transfer reaction. Examples of Bronsted-Lowry acids are HC1, NH4+, and HSO4- examples of Bronsted-Lowry bases are OH-, F-, and NH3. 

This theory was followed in 1884 by the first really comprehensive theory of acids and bases, produced by the Swedish chemist Svante Arrhenius (1859-1927). He suggested that since these acid solutions were electrolytes (see Chapter 5) their solutions contained many ions. According to Arrhenius theory, acids produce hydrogen ions (H+) when they dissolve in water, whereas bases produce hydroxide ions (OH ). 

According to the Arrhenius theory of acids and bases, a basic solution has more hydroxide ions than hydrogen ions. 

The Arrhenius theory is useful if you are interested in the ions that result when an acid or a base dissociates in water. It also helps explain what happens when an acid and a base undergo a neutralization reaction. In such a reaction, an acid combines with a base to form an ionic compound and water. Examine the following reactions ... 

There is yet another problem with the Arrhenius theory. It is limited to acid-base reactions in a single solvent, water. Many acid-base reactions take place in other solvents, however. 

In 1923, two chemists working independently of each other, proposed a new theory of acids and bases. (See Figure 10.4.) Johannes Bronsted in Copenhagen, Denmark, and Thomas Lowry in London, England, proposed what is called the Brpnsted-Lowry theory of acids and bases. This theory overcame the problems related to the Arrhenius theory. 

C99 Which of the following compounds is a base according to the Arrhenius theory ... 

Arrhenius theory hydronium ion Brpnsted-Lowry theory conjugate acid-base pair conjugate base conjugate acid strong acid weak acid strong base... 

Arrhenius theory of acids and bases the theory stating that an acid is a substance that produces hydrogen ions in water and a base is a substance that produces hydroxide ions in water (10.1)... 

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