Ion dissociation theory

For higher ionic strength, e g. highly saline waters the PITZER equation can be used (Pitzer 1973). This semi-empirical model is based also on the DEBYE-HUCKEL equation, but additionally integrates virial equations (vires = Latin for forces), that describe ion interactions (intermolecular forces). Compared with the ion dissociation theory the calculation is much more complicated and requires a... 

Fig. 4 to Fig. 8 show the severe divergence for activity coefficients such as given here for calcium, chloride, sulfate, sodium and water ions, calculated with different equations. The activity coefficients were calculated applying Eq. 13 to Eq. 17 for the corresponding ion dissociation theories, whereas the values for the PITZER equations were gained using the program PHRQPITZ. The limit of validity of each theory is clearly shown. 

The most common approach used by geochemical modeling codes to describe the water-gas-rock-interaction in aquatic systems is the ion dissociation theory outlined briefly in chapter 1.1.2.6.1. However, reliable results can only be expected up to ionic strengths between 0.5 and 1 mol/L. If the ionic strength is exceeding this level, the ion interaction theory (e.g. PITZER equations, chapter 1.1.2.6.2) may solve the problem and computer codes have to be based on this theory. The species distribution can be calculated from thermodynamic data sets using two different approaches (chapter 2.1.4) ... 

Furthermore, compared to the PHREEQC version from 1995, it was already possible to model kinetically controlled reactions with EQ 3/6. An advantage of EQ 3/6 over the recent PHREEQC version is that it can use both the ion dissociation theory and the PITZER equations for solutions with higher ionic strengths. 

For the species in solution (SOLUTIONSPECIES, Table 23), listed in the top row with current number, solubility constant log k and enthalpy delta h are given in kcal/mol or kJ/mol at a temperature of 25 °C. Using the sub-key-word gamma parameters for the calculation of the activity coefficient y according the WATEQ-DEBYE-HUCKEL ion dissociation theory (compare to chapter 1.1.2.6.1) are given. With the sub-key-word analytical , coefficients At to A5 are defined to calculate the temperature dependence of the solubility-product constant. 

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... 

Nernst s point of entry into ionic and electronic theories in chemistry, then, was electrolysis and solution theory, in the mainstream of the "Ionist" dissociation theory. Indeed, van t Hoff similarly proposed an ionic theory of the polar molecule in 1895, speculating on the binding forces between 0+ and O- ions in the 02 molecule. 114... 

Our application of this approach to the benzene ion dissociation in collaboration with Klippenstein was noted in Section II. When it can be carried out, this is by far the most satisfactory way currently available for extrapolation to E. The necessary VTST calculations, whether by way of the Marcus variational RRKM approach or other approaches (e.g., statistical adiabatic channel theory ) are laborious, involving the quantum chemical construction of large potential maps for the interaction of the separating fragments and extensive statistical calculations for the dissociation process. Application of this approach to a variety of interesting systems is one of the outstanding opportunities for future work. 

Phase space theory (PST) has been widely used for estimation of rates and energy partitioning for ion dissociations. It can be considered within the framework of transition-state theory as the limiting case of a loose transition state, in which all product degrees of freedom are statistically fully accessible at the transition state. As such, it is expected to give an upper limit for dissociation rates and to be best suited to barrierless dissociations involving reaction coordinates with simple bond cleavage character. 

He made major contributions to electrochemistry, thermodynamics, and photochemistry. Nernsfs early studies in electrochemistry were inspired by Arrhenius dissociation theory which first recognized the importance of ions in solution His heat theorem, known as the Third Law of Thermodynamics, was developed in 1906. In 1918 his studies of photochemistry led him to his atom chain reaction theory. In laoer years, he occupied himself with astrophysical theories, a field in w hich the heat theorem had important applications. 

Despite these strong assumptions, the Poisson-Boltzmann theory describes electric double layers surprisingly well. The reason is that errors lead to opposite effects and compensate each other. Including non-coulombic interactions leads to an increase of the ion concentration at the surface and a reduced surface potential. On the other hand, taking the finite size of the ions into account leads to a lower ion concentration at the surface and thus an increased surface potential. A reduction of the dielectric permittivity due to the electric field increases its range but at the same time reduces the surface potential because less ions dissociate or adsorb. 

Arrhenius acid-base theory - Arrhenius developed the theory of the electrolytic dissociation (1883-1887). According to him, an acid is a substance which delivers hydrogen ions to the solution. A base is a substance which delivers hydroxide ions to the solution. Accordingly, the neutralization reaction of an acid with a base is the formation of water and a salt. It is a so-called symmetrical definition because both, acids and bases must fulfill a constitutional criterion (presence of hydrogen or hydroxide) and a functional criterion (to deliver hydrogen ions or hydroxide ions). The theory could explain all of the known acids at that time and most of the bases, however, it could not explain the alkaline properties of substances like ammonia and it did not include the role of the solvent. -> Sorensen (1909) introduced the -> pH concept. 

Fig. 6 Comparison of the activity coefficient of SO42" in relation to the ionic strength as calculated using a Na2(S04) solution (aS04-2= 5.31, bS04-2= -0 07 Table 4) and different theories of ion dissociation and the PITZER equation, dashed lines signify calculated values outside the validity range of the corresponding ion dissociation equation.

Phosphoric acid was the original of the three water molecule type ,- replacement of these molecules by basic oxides in typical phosphates, investigated by Clark, led Graham to the theory of basicity. In aqueous solutions phosphoric acid has played a no less important part as an example of successive dissociation of hydrogen ions. The theory of isomorphism, enunciated by Mitscherlich and others, was founded on the phosphates and arsenates. 

The benzhydryl chlorides and BC13 react with formation of ion pairs (ionization constant, Ki) which dissociate to give the free ions (dissociation constant, KD). Because paired and free diarylcarbenium ions show only slightly different UV-visible spectra, [41], spectrophotometric measurements allow the determination of the total carbocation concentration. On the other hand, only free ions are detected by conductometric analysis, and a combination of both methods allows the determination of Ki and Kd using the theory of binary ionogenic equilibria [42,43]. 

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. 

Whilst for this case, without the aid of the dissociation theory, there is hardly anything to be said, that theory pictures a mutual action of the two acids which explains that the properties of the solutions—conductivity, rate of inversion of cane sugar, c.—are not the mean between those of two solutions containing the acids separately. When one acid is mixed with another, the increased quantity of H-ions causes a displacement of equilibrium which can be followed out numerically. 

Dissociation Theory.—According to Ostwald the color changes in phenolphthalein are explained as due to electrolytic dissociation, the negative ion of the salt being colored. In the phenolphthalein itself no dissociation occurs and the compound is thus colorless in neutral or acid solutions. When a salt is formed dissociation takes place and the colored ions produce a colored solution. This does not seem quite satisfactory in the case of the tri-sodium salt (p. 754) which evidently does not dissociate as the solution is colorless. This point is explained by the effect of the excess of alkali in retarding dissociation. 

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 ... 

The procedure is based upon the assumption that two different solutions have the same concentration of hydrogen ions if they produce equal color intensities of a given indicator. The simple dissociation theory of indicators provides that... 

Composition of Salts. A famous example of school-made misconceptions of our students arises from the Dissociation Theory of Arrhenius. In 1884, he postulated that salt molecules are found in solid salts as the smallest particles and decompose into ions by dissolving in water . Later, with the concept of electrons, the misconception that atoms of salt molecules form ions through electron exchange was born. Today, experts recognize that there are no salt molecules, that ions exist all the time - even in the solid salt. By dissolving the solid salt, water molecules surround the ions, and hydrated ions are not connected, they move freely in the salt solution. 

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