Thermodynamics reversible work

Notably, all theories for estimating the interfacial tension have been subjected to severe criticism. All theories have limitations and they should be used with care. Despite the problems and uncertainties associated with the component theories, the solid surface energies calculated from contact angles with these theories are often of practical importance in studies of wetting phenomena, surface modification and adhesion, e.g. for developing correlations between the practical work of adhesion with the thermodynamic/reversible work of adhesion, i.e. the work of adhesion calculated from the Young-Dupre equation (or based on interfacial tensions). 

Foams, like almost all systems containing two or more immiscible phases, involve thermodynamic conditions in which the primary driving force is to reduce the total interfacial area between the phases—that is, the systems are thermodynamically unstable. The amount of thermodynamically reversible work required to create an interface is given by... 

Figure III-l depicts a hypothetical system consisting of some liquid that fills a box having a sliding cover the material of the cover is such that the interfacial tension between it and the liquid is zero. If the cover is slid back so as to uncover an amount of surface dJl, the work required to do so will he ydSl. This is reversible work at constant pressure and temperature and thus gives the increase in free energy of the system (see Section XVII-12 for a more detailed discussion of the thermodynamics of surfaces).

The van der Waals and other non-covalent interactions are universally present in any adhesive bond, and the contribution of these forces is quantified in terms of two material properties, namely, the surface and interfacial energies. The surface and interfacial energies are macroscopic intrinsic material properties. The surface energy of a material, y, is the energy required to create a unit area of the surface of a material in a thermodynamically reversible manner. As per the definition of Dupre [14], the surface and interfacial properties determine the intrinsic or thermodynamic work of adhesion, W, of an interface. For two identical surfaces in contact ... 

This expression shows that the maximum possible useful work (i.e., reversible work) that can be obtained from any process occurring at constant temperature and pressure is a function of the initial and final states only and is independent of the path. The combination of properties U + PV - TS or H - TS occurs so frequently in thermodynamic analysis that it is given a special name and symbol, F, the free energy (sometimes called the Gibbs Free Energy). Using this definition, Equation 2-143 is written... 

Definition of Absolute Temperature.— The temperatures of two bodies are proportional to the quantities of heat respectively taken in and given out in localities at one temperature and at the other, respectively, by a material system subjected to a complete cycle of perfectly reversible thermodynamic operations, and not allowed to part with or take in heat at any other temperature or, the absolute values of two temperatures are to one another in the proportion of the heat taken in to the heat rejected in a perfect thermodynamic engine working with a source and refrigerator at the higher and lower of the temperatures respectively. ... 

Thermodynamically, the fracture energy is the sum of the reversible work (fF representing the reversible molecular interactions at the interface) and irreversible work (fVi, representing the irreversible deformation of the interfacial joint) both W, and fVi are expressed per unit area of the fracture energy by Eq. (9). 

Figure 10. Kleitz s reaction pathway model for solid-state gas-diffusion electrodes. Traditionally, losses in reversible work at an electrochemical interface can be described as a series of contiguous drops in electrical state along a current pathway, for example. A—E—B. However, if charge transfer at point E is limited by the availability of a neutral electroactive intermediate (in this case ad (b) sorbed oxygen at the interface), a thermodynamic (Nernstian) step in electrical state [d/j) develops, related to the displacement in concentration of that intermediate from equilibrium. In this way it is possible for irreversibilities along a current-independent pathway (in this case formation and transport of electroactive oxygen) to manifest themselves as electrical resistance. This type of chemical valve , as Kleitz calls it, may also involve a significant reservoir of intermediates that appears as a capacitance in transient measurements such as impedance. Portions of this image are adapted from ref 46. (Adapted with permission from ref 46. Copyright 1993 Rise National Laboratory, Denmark.)...

A hypothetical cycle for achieving reversible work, typically consisting of a sequence of operations (1) isothermal expansion of an ideal gas at a temperature T2 (2) adiabatic expansion from T2 to Ti (3) isothermal compression at temperature Ti and (4) adiabatic compression from Ti to T2. This cycle represents the action of an ideal heat engine, one exhibiting maximum thermal efficiency. Inferences drawn from thermodynamic consideration of Carnot cycles have advanced our understanding about the thermodynamics of chemical systems. See Carnot s Theorem Efficiency Thermodynamics... 

This is the maximum amount of useful work that can be derived from the system on driving the reaction in the opposite direction. Thus, Vrev corresponds to the reversible work and is consequently called the thermodynamic reversible potential. At 25°C and 1 bar, the AG for the water-splitting reaction is 237.178 kj/mol [10]. Therefore,... 

This is, in fact, the way electrode potentials are measured in practice. A cell is made up of the electrode of interest (the working electrode, e.g., Cu in Fig. 7.14) and a reference electrode made of Pt over which is bubbled Hj- No current passes through the reference electrode, which is therefore at its thermodynamically reversible potential. A counter-electrode (not shown in Fig. 7.14) is coupled through a power source... 

The distinction between reversible and irreversible work is one of the most important in thermodynamics. We shall first illustrate this distinction by means of a specific numerical example, in which a specified system undergoes a certain change of state by three distinct paths approaching the idealized reversible limit. Later, we introduce a formal definition for reversible work that summarizes and generalizes what has been learned from the path dependence in the three cases. In each case, we shall evaluate the integrated work w 2 from the basic path integral,... 

Consider a material or system that is not at equilibrium. Its extensive state variables (total entropy number of moles of chemical component, i total magnetization volume etc.) will change consistent with the second law of thermodynamics (i.e., with an increase of entropy of all affected systems). At equilibrium, the values of the intensive variables are specified for instance, if a chemical component is free to move from one part of the material to another and there are no barriers to diffusion, the chemical potential, q., for each chemical component, i, must be uniform throughout the entire material.2 So one way that a material can be out of equilibrium is if there are spatial variations in the chemical potential fii(x,y,z). However, a chemical potential of a component is the amount of reversible work needed to add an infinitesimal amount of that component to a system at equilibrium. Can a chemical potential be defined when the system is not at equilibrium This cannot be done rigorously, but based on decades of development of kinetic models for processes, it is useful to extend the concept of the chemical potential to systems close to, but not at, equilibrium. 

Thermodynamic considerations are applied to understand the processes of energy conversion in SOFCs. The reversible work of a fuel cell, represented by the Nemst voltage, can be calculated by the Gibbs free enthalpy of the reaction. The consideration of the electrical effects shows that the molar flow of the spent fuel is proportional to the electric current and that the reversible work is proportional to the reversible voltage. A coupling between the thermodynamic data and the electrical data is only possible by using the quantities power or heat flow and not by using work and heat. 

Consequently, the energy of the gas is constant for the isothermal reversible expansion or compression and, according to the first law of thermodynamics, the work done on the gas must therefore be equal but opposite in sign to the heat absorbed by the gas from the surroundings. For a reversible process the pressure must be the pressure of the gas itself. Therefore, we have for the isothermal reversible expansion of n moles of an ideal gas between the volumes F and V... 

Thomson applied the first law of thermodynamics to a virtual charge of magnitude 8Q passing through the circuit at equilibrium shown in Fig. 4. Equating the reversible work needed to drive the charge to the heat emitted gives... 

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