Slow Theory

In the absence of bulk flow one is led by arguments using a d)mamic version of the random phase approximation to an alternative expression to equation (4.4.11), in which it is the slow chains that dominate the kinetics (Brochard et al. 1983). This is sometimes referred to as the slow theory . There have been suggestions (Akcasu et al. 1992) that mutual diffusion should approach the slow-theory limit as the temperature is reduced towards the glass transition temperature of one of the components. A definitive solution to this problem awaits more work, both theoretical and experimental. 

In spite of considerable development of thermodynamics and molecular theory, most of the methods used today are empirical and their operation requires knowledge of experimental values. However, the rate of accumulation of experimental data seems to be slowing down even though the need for precise values is on the rise. It is then necessary to rely on methods said to be predictive and which are only estimates. 

Qualitative examples abound. Perfect crystals of sodium carbonate, sulfate, or phosphate may be kept for years without efflorescing, although if scratched, they begin to do so immediately. Too strongly heated or burned lime or plaster of Paris takes up the first traces of water only with difficulty. Reactions of this type tend to be autocat-alytic. The initial rate is slow, due to the absence of the necessary linear interface, but the rate accelerates as more and more product is formed. See Refs. 147-153 for other examples. Ruckenstein [154] has discussed a kinetic model based on nucleation theory. There is certainly evidence that patches of product may be present, as in the oxidation of Mo(lOO) surfaces [155], and that surface defects are important [156]. There may be catalysis thus reaction VII-27 is catalyzed by water vapor [157]. A topotactic reaction is one where the product or products retain the external crystalline shape of the reactant crystal [158]. More often, however, there is a complicated morphology with pitting, cracking, and pore formation, as with calcium carbonate [159]. 

To proceed with the topic of this section. Refs. 250 and 251 provide oversights of the application of contemporary surface science and bonding theory to catalytic situations. The development of bimetallic catalysts is discussed in Ref. 252. Finally, Weisz [253] discusses windows on reality the acceptable range of rates for a given type of catalyzed reaction is relatively narrow. The reaction becomes impractical if it is too slow, and if it is too fast, mass and heat transport problems become limiting. 

The result is that, to a very good approxunation, as treated elsewhere in this Encyclopedia, the nuclei move in a mechanical potential created by the much more rapid motion of the electrons. The electron cloud itself is described by the quantum mechanical theory of electronic structure. Since the electronic and nuclear motion are approximately separable, the electron cloud can be described mathematically by the quantum mechanical theory of electronic structure, in a framework where the nuclei are fixed. The resulting Bom-Oppenlieimer potential energy surface (PES) created by the electrons is the mechanical potential in which the nuclei move. Wlien we speak of the internal motion of molecules, we therefore mean essentially the motion of the nuclei, which contain most of the mass, on the molecular potential energy surface, with the electron cloud rapidly adjusting to the relatively slow nuclear motion. 

Note that the differential equation obtained from this approaeh will never agree perfeetly with the results of a simulation. The above fomuilation is essentially an adiabatie fomuilation of die proeess the spontaneous emission is eonsidered to be slow eompared with the time seale for the purity-preserving transformations generated by the external field, whieh is what allows us to assume m the theory that the external field... 

Hamiltonian, but in practice one often begins with a phenomenological set of equations. The set of macrovariables are chosen to include the order parameter and all otlier slow variables to which it couples. Such slow variables are typically obtained from the consideration of the conservation laws and broken synnnetries of the system. The remaining degrees of freedom are assumed to vary on a much faster timescale and enter the phenomenological description as random themial noise. The resulting coupled nonlinear stochastic differential equations for such a chosen relevant set of macrovariables are collectively referred to as the Langevin field theory description. 

In two classic papers [18, 46], Calm and Flilliard developed a field theoretic extension of early theories of micleation by considering a spatially inliomogeneous system. Their free energy fiinctional, equations (A3.3.52). has already been discussed at length in section A3.3.3. They considered a two-component incompressible fluid. The square gradient approximation implied a slow variation of the concentration on the... 

A situation that arises from the intramolecular dynamics of A and completely distinct from apparent non-RRKM behaviour is intrinsic non-RRKM behaviour [9], By this, it is meant that A has a non-random P(t) even if the internal vibrational states of A are prepared randomly. This situation arises when transitions between individual molecular vibrational/rotational states are slower than transitions leading to products. As a result, the vibrational states do not have equal dissociation probabilities. In tenns of classical phase space dynamics, slow transitions between the states occur when the reactant phase space is metrically decomposable [13,14] on the timescale of the imimolecular reaction and there is at least one bottleneck [9] in the molecular phase space other than the one defining the transition state. An intrinsic non-RRKM molecule decays non-exponentially with a time-dependent unimolecular rate constant or exponentially with a rate constant different from that of RRKM theory. 

Nikitin E E and UmanskiT S Ya 1984 Theory of Slow Atomic Collisions (Ber ir Springer)... 

The VER lifetime of liquid O2 is 280 ms at 70 K [82]. Predicting such a slow rate from theory is a fonnidable challenge taken up by Skinner and co-workers [54] in a recent paper. The fundamental frequency of O2 is 1552... 

Thus one must rely on macroscopic theories and empirical adjustments for the determination of potentials of mean force. Such empirical adjustments use free energy data as solubilities, partition coefficients, virial coefficients, phase diagrams, etc., while the frictional terms are derived from diffusion coefficients and macroscopic theories for hydrodynamic interactions. In this whole field of enquiry progress is slow and much work (and thought ) will be needed in the future. 

The golden rule is a reasonable prediction of state-crossing transition rates when those rates are slow. Crossings with fast rates are predicted poorly due to the breakdown of the perturbation theory assumption of a small interaction. 

Numerous theories exist as to how the Chilean deposits formed and survived. It has been postulated that the unique nitrate-rich caUche deposits of northern Chile owe their existence to an environment favorable to accumulation and preservation of the deposits, rather than to any unusual source of the saline materials (2). The essential conditions are an extremely arid climate similar to that of the Atacama desert in the 1990s, slow accumulation during the late Tertiary and Quaternary periods, and a paucity of nitrate-utilizing plants and soil microorganisms. 

---