The Arrhenius Theory

Aqueous solutions of most protic acids (those containing acidic hydrogen atoms) exhibit certain properties, which are properties of hydrated hydrogen ions in aqueous solution. 

Acids have a sour taste. Pickles are usually preserved in vinegar, a 5% solution of acetic acid. Many pickled condiments contain large amounts of sugar so that the taste of acetic acid is partially masked by the sweet taste of sugar. Lemons contain citric acid, which is responsible for their characteristic sour taste. 

Acids change the colors of many indicators (highly colored dyes whose colors depend on the acidic or basic character of the solution). Acids turn blue litmus red, and cause bromthymol blue to change from blue to yellow. 

Nonoxidizing acids react with metals above hydrogen in the activity series (see Section 6-8, Part 2) to liberate hydrogen gas, H2. (Nitric acid, HNO3, a common oxidizing acid, reacts with metals to produce primarily nitrogen oxides.) 

Acids react with (neutralize) metal oxides and metal hydroxides to form salts and water (see Section 6-8, Part 1). 

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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. 

Although the protonic theory is not confined to aqueous solutions, it does not cover aprotic solvents. The solvent system theory predates that of Bronsted-Lowry and represents an extension of the Arrhenius theory to solvents other than water. It may be represented by the defining equation ... 

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... 

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 ... 

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 ... 

The Arrhenius theory (above) was wholly empirical in terms of it derivation. A more rigorous, but related, form of the theory is that of Eyring (also called the theory of absolute reaction rates). The Eyring equation is... 

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 ... 

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 Arrhenius theory has limitations, however. For example, H (aq), a bare proton, does not exist in water. The positive charge on a proton is attracted to the region of negative charge on the lone pair of electrons on a water molecule s oxygen atom. The combination is a hydrated proton called a hydroniiun ion, HaO+faq)-... 

The Arrhenius theory also has limitations for explaining certain reactions. For example, aqueous solutions of ammonia are basic. They react with acids in neutralization reactions, even though ammonia does not contain the hydroxide ion. Many aqueous solutions of salts with no hydroxide ions are basic, too. Some reactions take place without any liquid solvent. For example, ammonium chloride can be formed by the reaction between ammonia and hydrogen chloride, which are both gases ... 

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. 

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. 

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

Question. Write out the equations for the statistical mechanical form, the thermodynamic form, collision theory and the Arrhenius theory. What are the equivalent terms ... 

There are two models that quantitatively describe the relationship between temperature and rate constants, the Arrhenius theory and the Eyring theory [2, 3], Engineers prefer the Arrhenius equation because it is slightly simpler, while kineti-cists prefer the Eyring equation because its parameters (entropy and enthalpy of activation, AS and AH, respectively) can be interpreted more directly. Here, we will use Eyring s equation. 

This is the same as Bronsted s theory which was designed particularly for solutions. The concentration of the activated complex can be expressed in terms of the reactants and the equilibrium constant K. Also the heat of the reaction, AH, to give the activated complex, can be calculated approximately from the quantum theory or from the Arrhenius theory. Since AF= —RT In K and AF = AII — TAS, and since K can, in some cases, be calculated from known, fundamental constants, the entropy term remains the only unknown. Rodebush has long pointed out that the unknown quantity 5 in the formula k = se E/RT is related to an entropy term. As a first approximation it has been related to a collision frequency in bimolecular reactions and to a vibration frequency in unimolecu-lar reactions. Combining the two thermodynamic equations23... 

According to the Arrhenius theory the decrease of A with increasing concentration of the solution with all electrolytes is merely due to the lowering of the dissociation degree as this theory does not take into account the mutual attraction of ions and the lowering of ion mobility in more concentrated solutions, the velocity of the ions in equation (111-25) should be equal both at finite concentrations and infinite dilution, i. e. ( + + v ) = (v + ). As... 

Scientists did not embrace the Arrhenius theory when they first heard about it during the 1880s. Why were they unimpressed with this theory What was necessary to convince them Arrhenius is featured on several web sites on the Internet. To link with these web sites, go to the web site above. Go to Science Resources, then to Chemistry 11 to find out where to go next. 

According to the Arrhenius theory, acids increase the concentration of H+ in aqueous solutions. Thus, an Arrhenius acid must contain hydrogen as the source of H+. You can see this in the dissociation reactions for acids on the previous page. 

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 ... 

HCl(aq) + NaOH(aq) —> NaCl(aq) + H2Om The net ionic equation for this reaction shows the principal ions in the Arrhenius theory. 

Problems arise with the Arrhenius theory, however. One problem involves the ion that is responsible for acidity H+. Look again at the equation for the dissociation of hydrochloric acid. 

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