Tendency theory

In an exposition of his tendency theory, Schonbein said there was in all cases in which an active cell is produced, a continuous series of electrolytic molecules having at both ends conducting bodies which have a strong attraction for the anion of the said molecules , and the chemical theory throws light on phenomena which the contact theory leaves in the dark. Schonbein said his tendency theory explained a difficulty for the chemical... 

Although Schonbein preferred his own tendency theory to the contact theory it was, he said, far from complete and the nature of electricity and its relations to chemical action (Chemismus) would have to be infinitely better known and more deeply investigated than they then were. His paper was never answered by the contactists but simply ignored as Ostwald said, the opposing parties had now talked themselves out and no further progress could be made until the meaning of Joule s experiments was imderstood. 

Two additional illustrations are given in Figures 6 and 7 which show fugacity coefficients for two binary systems along the vapor-liquid saturation curve at a total pressure of 1 atm. These results are based on the chemical theory of vapor-phase imperfection and on experimental vapor-liquid equilibrium data for the binary systems. In the system formic acid (1) - acetic acid (2), <() (for y = 1) is lower than formic acid at 100.5°C has a stronger tendency to dimerize than does acetic acid at 118.2°C. Since strong dimerization occurs between all three possible pairs, (fij and not... 

The shapes of covalent compounds are determined by the tendency for bonding pairs to be as far apart as possible whilst lone pairs have a greater effect than bonding pairs (VSEPR theory). 

The reactivity of the transition metals towards other elements varies widely. In theory, the tendency to form other compounds both in the solid state (for example reactions to form cations) should diminish along the series in practice, resistance to reaction with oxygen (due to formation of a surface layer of oxide) causes chromium (for example) to behave abnormally hence regularities in reactivity are not easily observed. It is now appropriate to consider the individual transition metals. 

A great number of monoaza or polyaza. either symmetrica] or unsym-metrical, mono trimethine thiazolocyainines have been synthesized in order to verify or to obtain semiempirical rules, more or less based on the resonance theory, concerning the relation between the color of a thiazolo dye and the number and place of nitrogen atoms in the chromophoric chain. For example. Forster s rule applies to ionic dyes and stipulates that the will increase with the decreasing tendency of chromophoric atoms lying between the two auxochromes to take up the characteristic charges (90). 

Nowadays there is a tendency to use the word term to describe that which arises from an approximate treatment of an electron configuration, whereas the word state is used to describe something that is observable experimentally. For example, we can say that the s 2s 2p 3d configuration of C gives rise to a term which, when spin-orbit coupling is taken into account, splits into Pi, 2 Pj, states. Since spin-orbit coupling can be excluded only in theory but never in practice there can be no experimental observation associated with the P term. ... 

The physical picture in concentrated electrolytes is more apdy described by the theory of ionic association (18,19). It was pointed out that as the solutions become more concentrated, the opportunity to form ion pairs held by electrostatic attraction increases (18). This tendency increases for ions with smaller ionic radius and in the lower dielectric constant solvents used for lithium batteries. A significant amount of ion-pairing and triple-ion formation exists in the high concentration electrolytes used in batteries. The ions are solvated, causing solvent molecules to be highly oriented and polarized. In concentrated solutions the ions are close together and the attraction between them increases ion-pairing of the electrolyte. Solvation can tie up a considerable amount of solvent and increase the viscosity of concentrated solutions. 

The lower the value of the more likely it is that S is positive indicating a thermodynamic tendency for the process to occur. Longitudinal wave theory has been appHed to the defoamer spreading process as in equation 5 where P is the penetration depth of a spreading droplet of initial radius R, viscosity Tj, and density p. 

The theory of crystal growth accordingly starts usually with the assumption that the atoms in the gaseous, diluted, or hquid mother phase will have a tendency to arrange themselves in a regular lattice structure. We ignore here for the moment the formation of poly crystalhne solids. In principle we should start with the quantum-mechanical basis of the formation of such lattice structures. Unfortunately, however, even with the computational effort of present computers with a performance of about 100 megaflops... 

The modern approach to chemical education appears to be strongly biased toward theories, particularly quantum mechanics. Many authors have remarked that classical chemistry and its invaluable predictive rules have been downgraded since chemistry was put into orbit around physics. School and undergraduate courses as well as textbooks show an increasing tendency to begin with the establishment of theoretical concepts such as orbitals and hybridization. There is a continuing debate in the chemical literature on the relative merits of theory as opposed to qualitative or descriptive chemistry 1-6). To quote the late J. J. Zucker-man who supported the latter approach (3). 

The problems which the orbital approximation raises in chemical education have been discussed elsewhere by the author (Scerri [1989], [1991]). Briefly, chemistry textbooks often fail to stress the approximate nature of atomic orbitals and imply that the solution to all difficult chemical problems ultimately lies in quantum mechanics. There has been an increassing tendency for chemical education to be biased towards theories, particularly quantum mechanics. Textbooks show a growing tendency to begin with the establishment of theoretical concepts such as atomic orbitals. Only recently has a reaction begun to take place, with a call for more qualitatively based courses and texts (Zuckermann [1986]). A careful consideration of the orbital model would therefore have consequences for chemical education and would clarify the status of various approximate theories purporting to be based on quantum mechanics. 

In many respects, this is the kernel of this book. For years it has not been too clear how one could consistently account for the wide variety of transition-metal chemistry in a way that does not conflict with the equally varied phenomena of spectroscopy and magnetochemistry that are so well rationalized by ligand-field theory. There is a tendency - psychologically quite natural, no doubt - for those interested in synthetic and mainstream chemistry not to look too closely at theory and physical properties, and, of course, vice versa. However, there has always been the need, surely, to build a logical synthesis of, or bridge between, these two aspects of the same subject. We hope that our presentation in this book goes some way towards providing that overview. 

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