Chapman mechanism, equations

Thermodynamic cycles are a useful way to understand energy release mechanisms. Detonation can be thought of as a cycle that transforms the unreacted explosive into stable product molecules at the Chapman-Jouguet (C-J) state,15 which is simply described as the slowest steady-state shock state that conserves mass, momentum, and energy (see Figure 1). Similarly, the deflagration of a propellant converts the unreacted material into product molecules at constant enthalpy and pressure. The nature of the C-J state and other special thermodynamic states important to energetic materials is determined by the equation of state of the stable detonation products. 

The next step is to determine the electrical charge and potential distribution in this diffuse region. This is done by using relevant electrostatic and statistical mechanical theories. For a charged planar surface, this problem was solved by Gouy (in 1910) and Chapman (in 1913) by solving the Poisson-Boltzmann equation, the so called Gouy-Chapman (G-C) model. 

In this project students review the Chapman cycle mechanism in detail and some photochemistry concepts including the photostationary state. A key element of this project is its focus on an important chemical mechanism and the use of exploratory options for predicting ozone concentrations as a function of time while reviewing other fundamental chemical kinetics concepts. Mathcad is used as the symbolic mathematics engine for solving the requisite differential equations and ample instruction is provided to students to guide them on the use of the software in this project. 

Modified Gouy-Chapman theory has been applied to soil particles for many years (Sposito, 1984, Chapter 5). It postulates only one adsorption mechanism -the diffuse-ion swarm - and effectively prescribes surface species activity coefficients through the surface charge-inner potential relationship contained implicitly in the Poisson-Boltzmann equation (Carnie and Torrie, 1984). Closed-form... 

S. L. Carnie, G.M. Torrie, The Statistical Mechanics of the Electrical Double Layer, Advan. Chem. Phys. 56 (1984) 141 253. (Gouy-Chapman and more advanced models, including integral equation theories, discrete charges, simulations.)... 

Using the theory developed by Chapman-Enskog (see Ref. 14), a hierarchy of continuum fluid mechanics formulations may be derived from the Boltzmann equation as perturbations to the Maxwellian velocity distribution function. The first three equation sets are well known (1) the Euler equations, in which the velocity distribution is exactly the Maxwellian form (2) the Navier-Stokes equations, which represent a small deviation from Maxwellian and rely on linear expressions for viscosity and thermal conductivity and (3) the Burnett equations, which include second order derivatives for viscosity and thermal conductivity. 

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