Electrolytic dissociation, theory

This system of nomenclature has withstood the impact of later experimental discoveries and theoretical developments that have since the time of Guyton de Morveau and Lavoisier greatiy altered the character of chemical thought, eg, atomic theory (Dalton, 1802), the hydrogen theory of acids (Davy, 1809), the duahstic theory (Berzehus, 1811), polybasic acids (Liebig, 1834), Periodic Table (Mendeleev and Meyer, 1869), electrolytic dissociation theory (Arrhenius, 1887), and electronic theory and modem knowledge of molecular stmcture. 

Hydrogen was recognized as the essential element in acids by H. Davy after his work on the hydrohalic acids, and theories of acids and bases have played an important role ever since. The electrolytic dissociation theory of S. A. Arrhenius and W. Ostwald in the 1880s, the introduction of the pH scale for hydrogen-ion concentrations by S. P. L. Sprensen in 1909, the theory of acid-base titrations and indicators, and J. N. Brdnsted s fruitful concept of acids and conjugate bases as proton donors and acceptors (1923) are other land marks (see p. 48). The di.scovery of ortho- and para-hydrogen in 1924, closely followed by the discovery of heavy hydrogen (deuterium) and... 

Svante August Arrhenius Sweden electrolytic dissociation theory... 

There is nothing new in principle about the use of isotopes as an aid to chemistry. For twenty years the radioactive elements have been used as indicators to study adsorption, solubility, volatility, distribution, and other phenomena of physical chemistry. Distribution of heavy radioactive atoms in plants has been studied through the relative amount of ionization found in the different parts. The ionization theory was supported by dissolving radioactive lead chloride in an aqueous solution of ordinary lead nitrate and then crystallizing out the lead chloride. The radioactive lead was found to be equally distributed between the two salts. In aqueous solution the two different kinds of lead are free to exchange anions, as predicted from the electrolytic dissociation theory. With un-ionized compounds of lead it was found that exchange does not take place. 

The Electrolytic Dissociation Theory. —From his studies of the conductances of aqueous solutions of acids and their chemical activity, Arrhenius (1883) concluded that an electrolytic solution contained two kinds of solute molecules these were supposed to be active molecules, responsible for electrical conduction and chemical action, and inactive molecules, respectively. It was believed that when an acid, base or salt was dissolved in water a considerable portion, consisting of the so-called active molecules, was spontaneously split up, or dissociated, into positive and negative ions it was suggested that these ions are free to move independently and are directed towards the appropriate electrodes under the influence of an electric field. The proportion of active, or dissociated, molecules to the total number of molecules, later called the degree of dissociation, was considered to vary with the concentration of the electrolyte, and to be equal to unity in dilute solutions. 

S) Electrolytic dissociation of water and hydrolysis. If one is not previously convinced of the correctness of the electrolytic dissociation theory, hardly any result won by means of it is so convincing as the agreement between the conclusions drawn in completely different ways as to the degree of dissociation of water itself. 

A method of this kind, dating from times when the electrolytic dissociation theory had not become accepted, rests on the following basis. To an electrolyte the relation... 

Raoult established his law by a large number of determinations in which the nature of solvent and solute were varied widely. The most characteristic of his results for dilute solutions are given in the following tables. The law was found to hold good in all cases, except aqueous solutions of salts. We shall see later that the exceptions can be accounted for satisfactorily by the electrolytic dissociation theory. 

The factor i only occurs in solutions which are good conductors of electricity, and in 1887 Arrhenius succeeded in explaining these apparent deviations from the simple laws by his electrolytic dissociation theory. The molecules of an electrolyte are broken up to a greater or less extent into their free ions, even when the solution is not conducting a current of electricity. Thus we have the equation HCl H - - CL... 

According to the electrolytic dissociation theory, electrolytes in aqueous solution are completely or partially dissociated into ions. Thus the acid HA splits into H+ ions and A ions, BOH into B+ and OH ions, and the salt BA into B+ ions and A ions. Hence equation (1) may be written more appropriately in the following form ... 

There is nothing m the simple form of the electrolytic dissociation theory which necessitates the conclusion that the 10ns and the undis-sociated molecules of an electrolyte should obey van t Hoff s law If they do not obey this law the law of mass action cannot be obeyed Hence the fact that solutions of strong electrolytes deviate fiom the requirements of the law of mass action is no argument against the theory of electrolytic dissociation 1... 

Hydrogen was recognized as the essential element in acids by H, Davy after his work on the hydrohalic acids, and theories of acids and bases have played an important role ever since. The electrolytic dissociation theory of... 

The study of catalysis by acids and bases played a very important part in the development of chemical kinetics, since many of the reactions studied in the early days of the subject were of this type. The early investigations of the kinetics of reactions catalyzed by acids and bases were carried out at the same time that,the electrolytic dissociation theory was being developed, and the kinetic studies contributed considerably to the development of that theory. The reactions considered from this, point of view were chiefly the inversion of cane sugar and the hydrolysis of esters. 

According to the views presented here, electrolytic dissociation is not the forerunner of chemical reactions and in fact chemical reactions do not depend upon the presence of ions as postulated in that theory. Certain physical properties of substances, which, early in the history of the electrolytic dissociation theory, were considered to be dependent upon, ionization, have since been shown to be independent of it. Thus, the color of a salt in solution was assumed to be made up of the different colors of the ions and the un-ionized molecule. Later work showed that ionization changes do not affect the color of the substance. Reference may be made here to a detailed review of these relations published by J. Lifschitz (Sammlung chemischer... 

Svante August Arrhenius (1859—1927), Swedish physicist and chemist. 1903 Nobel Prize laureate in chemistry on electrolytic dissociation theory. 

The symbol A (or A°) represents the maximum theoretical value that the molar conductivity of an electrolyte will approach when diluted indefinitely with an inert solvent. At the beginning of this century Kohlrausch found that the molar conductivity of salts in very dilute aqueous solutions showed a linear relation with the square root of the concentration. This, Kohlrausch s square root law , was incompatible with the Arrhenius electrolytic dissociation theory (q.v.), but it has since been justified by the Debye-Hiickel-Onsager theory of interionic attraction effects, which have been shown to have a dependence. 

Amplitude of a process, 114. Andrew s diagram, 173 Anisotropic bodies, 193 Aphorism of Clausius, 83, 92 Arrhenius theory of electrolytic dissociation, 301 Aschistic process, 31, 36, 51 Atmosphere, 39 Atomic energy, 26 Availability, 65, 66 Available energy, 66, 77, 80, 98, 101... 

The first substantial constitutive concept of acid and bases came only in 1887 when Arrhenius applied the theory of electrolytic dissociation to acids and bases. An acid was defined as a substance that dissociated to hydrogen ions and anions in water (Day Selbin, 1969). For the first time, a base was defined in terms other than that of an antiacid and was regarded as a substance that dissociated in water into hydroxyl ions and cations. The reaction between an acid and a base was simply the combination of hydrogen and hydroxyl ions to form water. 

Thus, quantitative criteria that could be tested experimentally had now been formulated for the first time in the theory of electrolytic dissociation, in contrast to earlier theories. The good agreement between degrees of dissociation calculated from independent measurements of two different properties with Eqs. (7.5) and... 

Soon after inception of the theory of electrolytic dissociation, it was shown that two types of componnds exist that can dissociate upon dissolution in water (or other solvents) ... 

The theory of electrolytic dissociation also provided the possibility for a transparent definition of the concept of acids and bases. According to the concepts of Arrhenius, an acid is a substance which upon dissociation forms hydrogen ions, and a base is a substance that forms hydroxyl ions. Later, these concepts were extended. 

The theory of electrolytic dissociation was not immediately recognized universally, despite the fact that it could qualitatively and quantitatively explain certain fundamental properties of electrolyte solutions. For many scientists the reasons for spontaneous dissociation of stable compounds were obscure. Thus, an energy of about 770kJ/mol is required to break up the bonds in the lattice of NaCl, and about 430kJ/mol is required to split H l bonds during the formation of hydrochloric acid solution. Yet the energy of thermal motions in these compounds is not above lOkJ/mol. It was the weak point of Arrhenius s theory that this mismatch could not be explained. 

Between 1865 and 1887, Dmitri 1. Mendeleev developed the chemical theory of solutions. According to this theory, the dissolution process is the chemical interaction between the solutes and the solvent. Upon dissolution of salts, dissolved hydrates are formed in the aqueous solution which are analogous to the solid crystal hydrates. In 1889, Mendeleev criticized Arrhenius s theory of electrolytic dissociation. Arrhenius, in turn, did not accept the idea that hydrates exist in solutions. 

According to modem views, the basic points of the theory of electrolytic dissociation are correct and were of exceptional importance for the development of solution theory. However, there are a number of defects. The quantitative relations of the theory are applicable only to dilute solutions of weak electrolytes (up to 10 to 10 M). Deviations are observed at higher concentrations the values of a calculated with Eqs. (7.5) and (7.6) do not coincide the dissociation constant calculated with Eq. (7.9) varies with concentration and so on. For strong electrolytes the quantitative relations of the theory are altogether inapplicable, even in extremely dilute solutions. 

Numerous measurements of the conductivity of aqueous solutions performed by the school of Friedrich Kohhansch (1840-1910) and the investigations of Jacobns van t Hoff (1852-1911 Nobel prize, 1901) on the osmotic pressure of solutions led the young Swedish physicist Svante August Arrhenius (1859-1927 Nobel prize, 1903) to establish in 1884 in his thesis the main ideas of his famous theory of electrolytic dissociation of acids, alkalis, and salts in solutions. Despite the sceptitism of some chemists, this theory was generally accepted toward the end of the centnry. 

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 elucidation of the electrical behavior of electrolytes owes much to Arrhenius, who was the originator of the theory of electrolytic dissociation, generally, known as the ionic theory. 

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 9. The V o/pH response of AI2O3 presented in a reduced fashion, to remove the dominant linear response Vo = Vo + 48(pi — 8) (mV). The various electrolytes at 0.1M concentration are 0 NaCl, A NaH2P04/Na2HP04, Merck buffer. Line a is the site-dissociation theory without counterion adsorption, and the other lines include various amounts of counterion adsorption. Reproduced with permission from Ref. (14). Copyright 1983, North Holland.

Louis Kahlenberg s Opposition to the Theory of Electrolytic Dissociation. Proc. Symposium on Selected Topics in the History of Electrochemistry, Geo. Dubpernell and J.H. Westbrook, eds. (Proc. vol. 78-6, 1978, The Electrochem. Society, Princeton, N.J.)>pp. 299-312. 

The theory of complete electrolytic dissociation at infinite dilution was developed by Debye and Hiickel (1923) and has been further extended by Onsager and later by Fuoss and Krauss. 

Such a chemical approach which links ionic conductivity with thermodynamic characteristics of the dissociating species was initially proposed by Ravaine and Souquet (1977). Since it simply extends to glasses the theory of electrolytic dissociation proposed a century ago by Arrhenius for liquid ionic solutions, this approach is currently called the weak electrolyte theory. The weak electrolyte approach allows, for a glass in which the ionic conductivity is mainly dominated by an MY salt, a simple relationship between the cationic conductivity a+, the electrical mobility u+ of the charge carrier, the dissociation constant and the thermodynamic activity of the salt with a partial molar free energy AG y with respect to an arbitrary reference state ... 

Ionic surfactants are electrolytes dissociated in water, forming an electrical double layer consisting of counterions and co-ions at the interface. The Gouy-Chapman theory is used to model the double layer. In conjunction with the Gibbs adsorption equation and the equations of state, the theory allows the surfactant adsorption and the related interfacial properties to be determined [9,10] (The Gibbs adsorption model is certainly simpler than the Butler-Lucassen-Reynders model for this case.). 

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