Volume-based thermodynamics approach

The author, as well as being an acclaimed teacher, is also an active researcher who has recently developed a new approach to thermodynamics (VBT - Volume Based Thermodynamics) published in high impact international journals, which is proving useful as a research tool. 

When both solutes and water traverse the same barrier, we should replace the classical thermodynamic approach with one based on irreversible thermodynamics. The various forces and fluxes are then viewed as interacting with each other, so the movement of water across a membrane influences the movement of solutes, and vice versa. Using this more general approach, we will show that the osmotic pressure difference effective in causing a volume flux across a membrane permeable to both water and solutes is generally less than the actual osmotic pressure difference across that membrane. 

More recently, Ustinov and coworkers [72, 73] developed a thermodynamic approach based on an equation of state to model the gas adsorption equilibrium over a wide range of pressure. Their model is based on the Bender equation of state, which is a virial-like equation with temperature dependent parameters based on the Benedict-Webb-Rubin equation of state [74]. They employed the model [75, 76] to describe supercritical gas adsorption on activated carbon (Norit Rl) at high temperature, and extended this treatment to subcritical fluid adsorption taking into account the phase transition in elements of the adsorption volume. They argued that parameters such as pore volume and skeleton density can be determined directly from adsorption measurements, while the conventional approach of He expansion at room temperature can lead to erroneous results due to the adsorption of He in narrow micropores of activated carbon. 

Other recently published correlative methods for predicting Tg include the group interaction modeling (GIM) approach of Porter (42), neural networks (43-45), genetic function algorithms (46), the CODESSA (acronym for Comprehensive Descriptors for Structural and Statistical Analysis ) method (47), the energy, volume, mass (EVM) approach (48,49), correlation to the results of semiempirical quantum mechanical calculations of the electronic structure of the monomer (50), and a method that combines a thermodynamic equation-of-state based on lattice fluid theory with group contributions (51). 

Equation (2) suggests that the volume fraction of crystalline material controls the microhardness value of a pol5mier. However, it was soon recognized the large influence of the crystalline lamellar thickness U upon microhardness in case of chain-folded and chain-extended polyethylene (PE) (4). Based on a thermodynamic approach, the dependence of hardness on the average crystal thickness was derived (15) ... 

The Gibbs thermodynamic approach, based on the consideration of the balance between volume and surface energies, gives an equation for the change in the free energy AG associated with formation of a spherical nucleus with radius p (Elwell and Scheel 1975) ... 

This approach is well known to us from a different part of the engineering knowledge base thermodynamics. For example, the pressure, P, of a volume, V, of gas is the average of the forces exerted by the individual molecules on the boundary of the volume, and the macroscopic behaviour of the gas is described by the simple equation PV = RT. This relationship between the three parameters P, V, and T holds as they change in time as part of some process, but the change must be slow compared to the timescale on which the microscopic collision processes take place, so that at any point in time, these microscopic processes experience essentially a static or equilibrium environment. 

Tables 6.13 and 6.14 list sets of internally consistent thermodynamic data for crystalline and liquid components, for use in equations 6.79 to 81. Although equations 6.80 and 6.81 are simply based on the Clausius-Clapeyron approach, Ghi-orso et al. (1983) use a semiempirical formulation for the volume of melt components. Its development is...

The goal of this research is to develop a new class of bioresponsive materials that undergo rapid, large-magnitude, volume-phase transitions in response to specific biological stimuli. Our approach to these materials is based on two fundamental aspects of hydrogels (1) hydrogel solvation/desolvation thermodynamics can be perturbed... and... 

There are a number of good choices, but you will not be completely satisfied with any textbook. 1 was not even completely satisfied when 1 used a textbook that I had written. You will probably choose a textbook that is compatible with your sequence of topics. There is at least one popular two-semester textbook that begins with quantum mechanics. (P) Most of the one-volume textbooks begin with thermodynamics but can accommodate different sequences. There are now physical chemistry textbooks that come in two or even four volumes, which provides for flexibility. In making your choice of textbook, you should consider clarity of presentation for the student. Because you are already familiar with die subject, this can be hard for you to judge. I once chose a textbook that seemed perfectly clear to me, but was not at all clear to the students. Next, you should consider the approach of the book. If you want to teach a more mathematically based course, you will probably decide to choose a textbook that uses this approach and not simply plan to provide supplementary information in class. 

In Section 3.4a we examine a model for the second virial coefficient that is based on the concept of the excluded volume of the solute particles. A solute-solute interaction arising from the spatial extension of particles is the premise of this model. Therefore the potential exists for learning something about this extension (i.e., particle dimension) for systems for which the model is applicable. In Section 3.4b we consider a model that considers the second virial coefficient in terms of solute-solvent interaction. This approach offers a quantitative measure of such interactions through B. In both instances we only outline the pertinent statistical thermodynamics a somewhat fuller development of these ideas is given in Flory (1953). Finally, we should note that some of the ideas of this section are going to reappear in Chapter 13 in our discussions of polymer-induced forces in colloidal dispersions and of coagulation or steric stabilization (Sections 13.6 and 13.7). 

Abstract An approach based on the theory of mixtures with the concept of molar volume fractions and on the basic principles of continuum mechanics and macroscopic thermodynamics is introduced to model soil freezing of solute saturated soil. 

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