Incomplete dissociation

A study of the concentration dependence of the molar conductivity, carried out by a number of authors, primarily F. W. G. Kohlrausch and W. Ostwald, revealed that these dependences are of two types (see Fig. 2.5) and thus, apparently, there are two types of electrolytes. Those that are fully dissociated so that their molecules are not present in the solution are called strong electrolytes, while those that dissociate incompletely are weak electrolytes. Ions as well as molecules are present in solution of a weak electrolyte at finite dilution. However, this distinction is not very accurate as, at higher concentration, the strong electrolytes associate forming ion pairs (see Section 1.2.4). 

The same conditions of equilibrium as given in Equations (11.153) and (11.155) are obtained when the vapor of the substance dissociates incompletely so that some monomeric species are present in the vapor. 

Ostwald s dilution law — A weak - electrolyte is dissociated incompletely upon dissolution in a solvent. The chemical equilibrium of dissociation of a weak acid HA into protons and acid anions is described by ... 

Antimicrobial activity, within a pharmaceutical context, is generally found only in the organic acids. These are weak acids and will therefore dissociate incompletely to give the three entities HA, H+ and A- in solution. As the undissociated form, HA, is the active antimicrobial agent, the ionization constant, Ka, is important and the pKa of the acid must be considered, especially in formulation of the agent. 

Dissociation of acids and bases depends very strongly on the solvent. The solvent SH ofren acts itself as an acid, and the strength of the dissolved base or acid depends on its acid-base properties. Acetonitrile is a weaker acid and base than water, its ion product being 3 10 . Therefore, in acetonitrile HBr, HCl, and H2SO4 dissociate incompletely, unlike their dissociation in water. In acetonitrile = 5.5 for HBr, 7.3 for H2SO4, and 8.9 for HCl. Thus, acetonitrile is a differentiating solvent. Carboxylic acids also dissociate in it to a lower extent than in water the difference between pAT of CH3CN and H2O is 14. 

If Q values actually reflect the primaiy medium effect of 0 , they cause that the above-mentioned melts as extremely aggressive acidic media, likely because of performance of anhydrous sulfuric acid in comparison with water (Hq -logy + = -11 In particular, such melts should completely dissolve appreciable quantities of solid oxides, e g., MgO, NiO, etc., up to 1 mol kg. For instance, MgO, which is practically insoluble in KCl-NaCl equimolar mixture (pK = 9.33 0.06 can be characterized by pK 1 (because 9.33 - 8 1) in KCl-LiCl eutectic that corresponds to the value of the solubility product of the order of 10". As for the KCl-NaCl-CaCl2 melt, the solubiUty product value should also be close to 1. On the contrary, most metal oxides slightly soluble in the KCl-NaCl melt were shown by Shapoval, Makogon and Pertchik to remain only slightly soluble in KCl-LiCl eutectic. Moreover, these oxides (NiO, CoO) are dissociated incompletely under these conditions. ... 

In a weak electrolyte (e.g. an aqueous solution of acetic acid) the solute molecules AB are incompletely dissociated into ions and according to the familiar chemical equation... 

Combinatorial Hbraries are limited by the number of sequences that can be synthesized. For example, a Hbrary consisting of one molecule each of a 60-nucleotide sequence randomized at each position, would have a mass of >10 g, weU beyond the capacity for synthesis and manipulation. Thus, even if nucleotide addition is random at all the steps during synthesis of the oligonucleotide only a minority of the sequences can be present in the output from a laboratory-scale chemical DNA synthesis reaction. In analyzing these random but incomplete Hbraries, the protocol is efficient enough to allow selection of aptamers of lowest dissociation constants (K ) from the mixture after a small number of repetitive selection and amplification cycles. Once a smaller population of oligonucleotides is amplified, the aptamer sequences can be used as the basis for constmcting a less complex Hbrary for further selection. 

Complete and Incomplete Ionic Dissociation. Brownian Motion in Liquids. The Mechanism of Electrical Conduction. Electrolytic Conduction. The Structure of Ice and Water. The Mutual Potential Energy of Dipoles. Substitutional and Interstitial Solutions. Diffusion in Liquids. 

Complete and Incomplete Ionic Dissociation. In the foregoing chapter mention has been made of electrolytes that are completely dissociated in solution, and of weak electrolytes where free ions are accompanied by a certain proportion of neutral molecules. In the nineteenth century it was thought that aqueous solutions of even the strongest electrolytes contained a small proportion of neutral molecules. Opinion as to the relation between strong and weak electrolytes has passed through certain vicissitudes and we shall describe later how this problem has been resolved. 

The Contact between Solvent and Solute Particles Molecules and Molecular Ions in Solution. Incomplete Dissociation into Free Ions. Proton Transfers in Solution. Stokes s Law. The Variation of Electrical Conductivity with Temperature. Correlation between Mobility and Its Temperature Coefficient. Electrical Conductivity in Non-aqueous Solvents. Electrical Conduction by Proton Jumps. Mobility of Ions in D20. 

Incomplete Dissociation into Free Ions. As is well known, there are many substances which behave as a strong electrolyte when dissolved in one solvent, but as a weak electrolyte when dissolved in another solvent. In any solvent the Debye-IIiickel-Onsager theory predicts how the ions of a solute should behave in an applied electric field, if the solute is completely dissociated into free ions. When we wish to survey the electrical conductivity of those solutes which (in certain solvents) behave as weak electrolytes, we have to ask, in each case, the question posed in Sec. 20 in this solution is it true that, at any moment, every ion responds to the applied electric field in the way predicted by the Debye-Hiickel theory, or does a certain fraction of the solute fail to respond to the field in this way In cases where it is true that, at any moment, a certain fraction of the solute fails to contribute to the conductivity, we have to ask the further question is this failure due to the presence of short-range forces of attraction, or can it be due merely to the presence of strong electrostatic forces ... 

At higher concentrations the Raman spectra of aqueous solutions of alkali nitrates and of nitric acid have been investigated. Nitric acid was found to be incompletely dissociated, though for the alkali nitrates no evidence of incomplete dissociation was found. Since accurate measurements on solutions of nitric acid have not been made at concentrations below 4.0 molar, it is not certain how the extrapolation to infinite... 

It is found that IIC1 is likewise incompletely dissociated in formic acid solution. There do not appear to be any accurate data on the degree of dissociation so we do not know whether it is necessary to place the proton level of HC1 below that of (H30)+ in formic acid solution. 

The most common hydrogen halides are HF (U.S. production = 3 X 108 kg/yr) and HC1 (3 X 109 kg/yr). They are most familiar as water solutions, referred to as hydrofluoric acid and hydrochloric acid, respectively. Recall (Chapter 13) that hydrofluoric acid is weak, incompletely dissociated in water, whereas HCl is a strong acid. 

Stable compound formation. This leads to incomplete dissociation of the... 

The nature of the first type of thermal reactions is as yet only speculative. The two obvious possibilities seem to be (1) reaction of an incomplete molecule (radical) with an unbound nearby ligand, made available by recoil fragmentation, radiolysis, chemical dissociation, or the presence of an external atmosphere and (2) reaction of the moiety with a nearby molecule to abstract a ligand. The first type with an external source of CO has been clearly demonstrated for the case of the Group VI carbonyls which, when heated in an atmosphere of CO (up to 100 atm pressure) showed a marked increase in yield. A much smaller enhancement of yield in vacuo was attributed (99) to radiolytic dissociation, because of the influence of irradiation at various y-fluxes. The alternative possibility—that of equilibrium dissociation of Cr(CO)6 in the solid state—has not been investigated. 

The above scheme satisfies much of the metabolic data however, some of it is speculative, and it is certainly incomplete. The evidence for the formation of the a-hydroxylated intermediate is circumstantial. The acetate ester of a-hydroxylated dimethylnitrosamine has been prepared (12.13) and has been found to be a potent, directly acting carcinogen (14). Other esters of a variety of a-hydroxylated nitros-amines have also been prepared (15). While it has been shown that DMN acetate is hydrolyzed to hydroxymethylmethyl-nitrosamine by an esterase enzyme, it has been pointed out that these derivatives of the a-hydroxylated nitrosamines also dissociate to N-nitrosoimmonium ions (15 16). 

For strong electrolytes, the activity of molecules cannot be considered, as no molecules are present, and thus the concept of the dissociation constant loses its meaning. However, the experimentally determined values of the dissociation constant are finite and the values of the degree of dissociation differ from unity. This is not the result of incomplete dissociation, but is rather connected with non-ideal behaviour (Section 1.3) and with ion association occurring in these solutions (see Section 1.2.4). 

Interionic forces are relatively less important for weak electrolytes because the concentrations of ions are relatively rather low as a result of incomplete dissociation. Thus, in agreement with the classical (Arrhenius) theory of weak electrolytes, the concentration dependence of the molar conductivity can be attributed approximately to the dependence of the degree of dissociation a on the concentration. If the degree of dissociation... 

If a solute of the general formula AX (A is the chiral ion and X is an achiral ion) dissociates completely into ions once dissolved, then the solubility of the racemic conglomerate, SR, is equal to n%V2-SA (where SA is concentration of A in a solution saturated with AX ). If the solute is of the type AX, then 5 = V2-5a. The subscript n refers to the achiral ion and may be fractional, and so A2X must be represented by AXi/. If dissociation of AX is incomplete, SA lies between n i/2-SA and 2SA. For weakly dissociated electrolytes (such as carboxylic acids), SR is approximately 2SA. 

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