Boltzmann equation, solution

The popular problems of kinetics theory is the derivation of hydrodynamic equations, in certain conditions, solution of f (r, v,t) transport equation is similar the form that can relate directly to continuous or hydrodynamic description. In certain conditions the transport process is like hydrodynamic limit. In 1911 David Hilbert was who ptropwsed the existence Boltzmann equations solutions (named normal solutions), and these are determinate by initial values of hydrodynamic variables it return to collision invariant (mass, momentum and kinetics energy), Sydney Chapman and David Enskog in 1917 were whose imroUed a systematic process for derivate the hydrodynamic equations (and their corrections of superior order) for these variables. 

Marmur [12] has presented a guide to the appropriate choice of approximate solution to the Poisson-Boltzmann equation (Eq. V-5) for planar surfaces in an asymmetrical electrolyte. The solution to the Poisson-Boltzmann equation around a spherical charged particle is very important to colloid science. Explicit solutions cannot be obtained but there are extensive tabulations, known as the LOW tables [13]. For small values of o, an approximate equation is [9, 14]... 

A3.1.3.2 THE CHAPMAN-ENSKOG NORMAL SOLUTIONS OF THE BOLTZMANN EQUATION... 

Fig. 1. Explanation of the principles of the finite-difference method for solution of the Poisson-Boltzmann equation...

Tanford, C., Kirkwood, J. G. Theory of protein titration curves. I. General equations for impenetrable spheres. J. Am. Chem. Soc. 79 (1957) 5333-5339. 6. Garrett, A. J. M., Poladian, L. Refined derivation, exact solutions, and singular limits of the Poisson-Boltzmann equation. Ann. Phys. 188 (1988) 386-435. Sharp, K. A., Honig, B. Electrostatic interactions in macromolecules. Theory and applications. Ann. Rev. Biophys. Chem. 19 (1990) 301-332. 

Another way of calculating the electrostatic component of solvation uses the Poisson-Boltzmann equations [22, 23]. This formalism, which is also frequently applied to biological macromolecules, treats the solvent as a high-dielectric continuum, whereas the solute is considered as an array of point charges in a constant, low-dielectric medium. Changes of the potential within a medium with the dielectric constant e can be related to the charge density p according to the Poisson equation (Eq. (41)). 

If there are ions in the solution, they will try to change their location according to the electrostatic potential in the system. Their distribution can be described according to Boltzmarm. Including these effects and applying some mathematics leads to the final linearized Poisson-Boltzmann equation (Eq. (43)). 

Application of the Boltzmann equation to Eq. (8.33) gives the entropy of the mixture according to this model for concentrated solutions ... 

In order to calculate the distribution function must be obtained in terms of local gas properties, electric and magnetic fields, etc, by direct solution of the Boltzmann equation. One such Boltzmann equation exists for each species in the gas, resulting in the need to solve many Boltzmann equations with as many unknowns. This is not possible in practice. Instead, a number of expressions are derived, using different simplifying assumptions and with varying degrees of vaUdity. A more complete discussion can be found in Reference 34. 

Since the solution of a system of Boltzmann equations for a many-component system is very similar to that for a simple gas, only the latter shall be discussed. 

Boltzmann s H-Theorem. —One of the most striking features of transport theory is seen from the result that, although collisions are completely reversible phenomena (since they are based upon the reversible laws of mechanics), the solutions of the Boltzmann equation depict irreversible phenomena. This effect is most clearly seen from a consideration of Boltzmann s IZ-function, which will be discussed here for a gas in a uniform state (no dependence of the distribution function on position and no external forces) for simplicity. 

Hydrodynamic Equations.—Before deriving the hydro-dynamic equations, some integral theorems that are useful in the solution of the Boltzmann equation will be proved. Consider a function of velocity, G(Vx), which may also be a function of position and time let... 

The Burnett Expansion.—The Chapman-Enskog solution of the Boltzmann equation can be most easily developed through an expansion procedure due to Burnett.15 For the distribution function of a system that is close to equilibrium, we may use as a zeroth approximation a local equilibrium distribution function given by the maxwellian form ... 

Chapman-Enskog Solution.—The solution of the Boltzmann equation obtained by Chapman and Enskog involves the assumption... 

Block relaxation, 61 Bogoliubov, N., 322,361 Boltzmann distribution, 471 Boltzmann equation Burnett method of solution, 25 Chapman-Enskog method of solution, 24... 

The outer layer (beyond the compact layer), referred to as the diffuse layer (or Gouy layer), is a three-dimensional region of scattered ions, which extends from the OHP into the bulk solution. Such an ionic distribution reflects the counterbalance between ordering forces of the electrical field and the disorder caused by a random thermal motion. Based on the equilibrium between these two opposing effects, the concentration of ionic species at a given distance from the surface, C(x), decays exponentially with the ratio between the electro static energy (zF) and the thermal energy (R 7). in accordance with the Boltzmann equation ... 

To understand this in more detail, we can consider the liquid to be based on a lattice arrangement. For low molar mass solutes, each point in the lattice can be considered to be occupied by either a solvent or solute molecule. The possible arrangements of solute and solvent molecules in an extensive lattice will be very large, as shown in Figure 5.1a. According to the Boltzmann equation. 

Since the middle of the 1990s, another computation method, direct simulation Monte Carlo (DSMC), has been employed in analysis of ultra-thin film gas lubrication problems [13-15]. DSMC is a particle-based simulation scheme suitable to treat rarefied gas flow problems. It was introduced by Bird [16] in the 1970s. It has been proven that a DSMC solution is an equivalent solution of the Boltzmann equation, and the method has been effectively used to solve gas flow problems in aerospace engineering. However, a disadvantageous feature of DSMC is heavy time consumption in computing, compared with the approach by solving the slip-flow or F-K models. This limits its application to two- or three-dimensional gas flow problems in microscale. In the... 

Figure 2.2 Non-dimensionalized velocity distribution across a channel for Kn = 0.1 (left) and Kn = 2.0 (right), taken from [2]. The results were obtained by DSCM using two different collision cross-sections and by solution of the linearized Boltzmann equation.

This theory of the diffuse layer is satisfactory up to a symmetrical electrolyte concentration of 0.1 mol dm-3, as the Poisson-Boltzmann equation is valid only for dilute solutions. Similarly to the theory of strong electrolytes, the Gouy-Chapman theory of the diffuse layer is more readily applicable to symmetrical rather than unsymmetrical electrolytes. 

Holst, M.J. Baker, N.A. Wang, F., Adaptive multilevel finite element solution of the Poisson-Boltzmann equation I algorithms and examples, J. Comp. Chem. 2000, 21, 1319-1342... 

Two remaining problems relating to the treatment of solvation include the slowness of Poisson-Boltzmann calculations, when these are used to treat electrostatic effects, and the difficulty of keeping buried, explicit solvent in equilibrium with the external solvent when, e.g., there are changes in nearby solute groups in an alchemical simulation. Faster methods for solving the Poisson-Boltzmann equation by means of parallel finite element techniques are becoming available, however.22 24... 

The electrostatic methods just discussed suitable for nonelectrolytic solvent. However, both the GB and Poisson approaches may be extended to salt solutions, the former by introducing a Debye-Huckel parameter67 and the latter by generalizing the Poisson equation to the Poisson-Boltzmann equation.68 The Debye-Huckel modification of the GB model is valid to much higher salt concentrations than the original Debye-Huckel theory because the model includes the finite size of the solute molecules. 

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