Thermodynamics in aqueous solutions

Frank HS, Evans MW (1945) Free volume and entropy in condensed systems. III. Entropy in binary liquid mixtures partial molal entropy in dilute solutions structure and thermodynamics in aqueous solutions. J Chem Phys 13 507-532... 

Hydrogen chloride is completely ionized in aqueous solutions at all but the highest concentrations. Thermodynamic functions have been deterrnined electrochemicaHy for equations 7 and 8. Values are given in Table 7. 

The activity of the hydrogen ion is affected by the properties of the solvent in which it is measured. Scales of pH only apply to the medium, ie, the solvent or mixed solvents, eg, water—alcohol, for which the scales are developed. The comparison of the pH values of a buffer in aqueous solution to one in a nonaqueous solvent has neither direct quantitative nor thermodynamic significance. Consequently, operational pH scales must be developed for the individual solvent systems. In certain cases, correlation to the aqueous pH scale can be made, but in others, pH values are used only as relative indicators of the hydrogen-ion activity. 

The chemistry of plutonium ions in solution has been thoroughly studied and reviewed (30,94—97). Thermodynamic properties of aqueous ions of Pu are given in Table 8 and in the Uterature (64—66). The formal reduction potentials in aqueous solutions of 1 Af HCIO or KOH at 25°C maybe summarized as follows (66,86,98—100) ... 

Each reactant and product appears in the Nemst equation raised to its stoichiometric power. Thermodynamic data for cell potentials have been compiled and graphed (3) as a function of pH. Such graphs are known as Pourbaix diagrams, and are valuable for the study of corrosion, electro deposition, and other phenomena in aqueous solutions.Erom the above thermodynamic analysis, the cell potential can be related to the Gibbs energy change... 

A large programme utilizing temperature-jump relaxation methods for the study of tautomerism in aqueous solution has led the Dubois group to determine the kinetic and thermodynamic parameters of the equilibrium (130a) (130b) (78T2259). The tautomeric... 

Studies on metal-pyrazole complexes in solution are few. The enthalpy and entropy of association of Co(II), Ni(II), Cu(II) and Zn(II) with pyrazole in aqueous solution have been determined by direct calorimetry (81MI40406). The nature of the nitrogen atom, pyridinic or pyrrolic, involved in the coordination with the metal cannot be determined from the available thermodynamic data. However, other experiments in solution (Section 4.04.1.3.3(i)) prove conclusively that only the N-2 atom has coordinating capabilities. 

The values given in the following table for the heats and free energies of formation of inorganic compounds are derived from a) Bichowsky and Rossini, Thermochemistry of the Chemical Substances, Reinhold, New York, 1936 (h) Latimer, Oxidation States of the Elements and Their Potentials in Aqueous Solution, Prentice-Hall, New York, 1938 (c) the tables of the American Petroleum Institute Research Project 44 at the National Bureau of Standards and (d) the tables of Selected Values of Chemical Thermodynamic Properties of the National Bureau of Standards. The reader is referred to the preceding books and tables for additional details as to methods of calculation, standard states, and so on. 

Scales for bases that are too weak to study in aqueous solution employ other solvents but are related to the equilibrium in aqueous solution. These equilibrium constants provide a measure of thermodynamic basicity, but we also need to have some concept of kinetic basicity. For the reactions in Scheme 5.4, for example, it is important to be able to make generalizations about the rates of competing reactions. 

In the discussion of the relative acidity of carboxylic acids in Chapter 1, the thermodynamic acidity, expressed as the acid dissociation constant, was taken as the measure of acidity. It is straightforward to determine dissociation constants of such adds in aqueous solution by measurement of the titration curve with a pH-sensitive electrode (pH meter). Determination of the acidity of carbon acids is more difficult. Because most are very weak acids, very strong bases are required to cause deprotonation. Water and alcohols are far more acidic than most hydrocarbons and are unsuitable solvents for generation of hydrocarbon anions. Any strong base will deprotonate the solvent rather than the hydrocarbon. For synthetic purposes, aprotic solvents such as ether, tetrahydrofuran (THF), and dimethoxyethane (DME) are used, but for equilibrium measurements solvents that promote dissociation of ion pairs and ion clusters are preferred. Weakly acidic solvents such as DMSO and cyclohexylamine are used in the preparation of strongly basic carbanions. The high polarity and cation-solvating ability of DMSO facilitate dissociation... 

Recently Stamhuis et al. (33) have determined the base strengths of morpholine, piperidine, and pyrrolidine enamines of isobutyraldehyde in aqueous solutions by kinetic, potentiometric, and spectroscopic methods at 25° and found that these enamines are 200-1000 times weaker bases than the secondary amines from which they are formed and 30-200 times less basic than the corresponding saturated tertiary enamines. The baseweakening effect has been attributed to the electron-withdrawing inductive effect of the double bond and the overlap of the electron pair on the nitrogen atom with the tt electrons of the double bond. It was pointed out that the kinetic protonation in the hydrolysis of these enamines occurs at the nitrogen atom, whereas the protonation under thermodynamic control takes place at the -carbon atom, which is, however, dependent upon the pH of the solution (84,85). The measurement of base strengths of enamines in chloroform solution show that they are 10-30 times weaker bases than the secondary amines from which they are derived (4,86). 

The acid-base classificationd l turns essentially on the thermodynamic properties of hydroxides in aqueous solution, since oxides themselves are not soluble as such (p. 630). Oxides may be ... 

The oxidizing power of the halate ions in aqueous solution, as measured by their standard reduction potentials (p. 854), decreases in the sequence bromate > chlorate > iodate but the rates of reaction follow the sequence iodate > bromate > chlorate. In addition, both the thermodynamic oxidizing power and the rate of reaction depend markedly on the hydrogen-ion concentration of the solution, being substantially greater in acid than in alkaline conditions (p, 855). 

Table 1.7 shows typical half reactions for the oxidation of a metal M in aqueous solutions with the formation of aquo cations, solid hydroxides or aquo anions. The equilibrium potential for each half reaction can be evaluated from the chemical potentials of the species involved see Appendix 20.2) and it should be noted that there is no difference thermodynamically between equations 2(a) and 2(b) nor between 3(a) and 3(b) when account is taken of the chemical potentials of the different species involved. 

The factors leading to the high resistance of the noble metals to chemical attack, i.e. their thermodynamic stability over a wide range of conditions and the possibility of the formation of very thin protective films under oxidising conditions, have already been mentioned. A factor tending to reduce corrosion resistance in aqueous solutions is the tendency of these metals to form complexes with some anions. 

Immunity the state of a metal whose corrosion rate is low or negligible because its potential is below (less positive than) that of equilibrium with a very small concentration (or activity of its dissolved ions. The metal is thus regarded as thermodynamically stable. Pourbaix has suggested that the small metal ion concentration be 10 mol dm (Atlas of Electrochemical Equilibria in Aqueous Solutions, p. 71, Pergamon/ CEBELCOR, Oxford (1966)). 

Water plays a crucial role in the inclusion process. Although cyclodextrin does form inclusion complexes in such nonaqueous solvents as dimethyl sulfoxide, the binding is very weak compared with that in water 13 Recently, it has been shown that the thermodynamic stabilities of some inclusion complexes in aqueous solutions decrease markedly with the addition of dimethyl sulfoxide to the solutions 14,15>. Kinetic parameters determined for inclusion reactions also revealed that the rate-determining step of the reactions is the breakdown of the water structure around a substrate molecule and/or within the cyclodextrin cavity 16,17). 

The relationship of thermodynamic functions of selective bonding of Hb to a series of carboxylic CP in the variation of the degree of ionization of carboxylic groups is expressed by the effect of enthalpy-entropy compensation (Fig. 18). The compensation effect of enthalpy and entropy components is the most wide-spread characteristic of many reactions in aqueous solutions for systems with a cooperative change in structure [78],... 

Thermodynamics of the stepwise formation of metal ion complexes in aqueous solution. S. Ahrland, Struct. Bonding (Berlin), 1973,15,167-188 (86). 

Recall that from the perspective of thermodynamics, every concentration is measured relative to a defined standard concentration. For any gas, the defined standard is 1 bar pressure for any solute in aqueous solution, the defined standard is 1 M. We treat the concentration terms in equilibrium constant expressions in this same way. 

---