Fluid system thermodynamic properties

Verlet, L. Computer experiments on classical fluids. I. Thermodynamical properties of Lennard-Jones molecules. Phys. Rev. 165 (1967) 98-103. Ryckaert, J.-P., Ciccotti,G., Berendsen, H.J.C. Numerical integration of the cartesian equations of motion of a system with constraints Molecular dynamics of n-alkanes. Comput. Phys. 23 (1977) 327-341. 

The phase rule specifies the number of intensive properties of a system that must be set to estabUsh all other intensive properties at fixed values (3), without providing information about how to calculate values for these properties. The field of appHed engineering thermodynamics has grown out of the need to assign numerical values to thermodynamic properties within the constraints of the phase rule and fundamental laws. In the engineering disciplines there is a particular demand for physical properties, both for pure fluids and mixtures, and for phase equiUbrium data (4,5). 

Postiilate 5 affirms that the other molar or specific thermodynamic properties of PVT systems, such as internal energy U and entropy S, are also functions of temperature, pressure, and composition. Tnese molar or unit-mass properties, represented by the plain symbols U, and S, are independent of system size and are called intensive. Temperature, pressure, and the composition variables, such as mole fraction, are also intensive. Total-system properties (V U S ) do depend on system size, and are extensive. For a system containing n moles of fluid, M = nM, where M is a molar property. 

Partial Molar Properties Consider a homogeneous fluid solution comprised of any number of chemical species. For such a PVT system let the symbol M represent the molar (or unit-mass) value of any extensive thermodynamic property of the solution, where M may stand in turn for U, H, S, and so on. A total-system property is then nM, where n = Xi/i, and i is the index identifying chemical species. One might expect the solution propei fy M to be related solely to the properties M, of the pure chemical species which comprise the solution. However, no such generally vahd relation is known, and the connection must be establi ed experimentally for eveiy specific system. 

Starling, Kenneth E., Fluid Thermodynamic Properties for Light Parol,-um Systems, Houston, TX Gulf Publishing Company, 1973. 

Finally, in this part of the work we would like to discuss to some extent practical tools to obtain thermodynamic properties of adsorbed fluids. We have mentioned above that the compressibility equation is the only simple recipe, for the moment, to obtain the thermodynamics of partly quenched simple fluids. The reason is that the virial equation is difficult to implement it has not been tested for partly quenched systems. Nevertheless, for the sake of completeness, we present the virial equation in the form [22,25]... 

Figure 11-26. Vapor pressure curve for ethylene refrigerant. (Used by permission Starling, K. E. Fluid Thermodynamic Properties for Light Petroleum Systems, 1973. Gulf Publishing Co., Houston, Texas. All rights reserved.)...

Starling, K. D., Fluid Thermodynamic Properties for Light Petroleum Systems, Gulf Publishing Co. (1973). 

It is necessary to be able to calculate the energy and momentum of a fluid at various positions in a flow system. It will be seen that energy occurs in a number of forms and that some of these are influenced by the motion of the fluid. In the first part of this chapter the thermodynamic properties of fluids will be discussed. It will then be seen how the thermodynamic relations are modified if the fluid is in motion. In later chapters, the effects of frictional forces will be considered, and the principal methods of measuring flow will be described. 

Fig. 2.37. Phase diagram for Ca0-Na20 Si02-(Al203)-H20 system in equilibrium with quartz at 400°C and 400 bars. Plagioclase solid solution can be represented by the albite and anorthite fields, whereas epidote is represented by clinozoisite. Note that the clinozoisite field is adjacent to the anorthite field, suggesting that fluids with high Ca/(H+) might equilibrate with excess anorthite by replacing it with epidote. The location of the albite-anorthite-epidote equilibrium point is a function of epidote and plagioclase composition and depends on the model used for calculation of the thermodynamic properties of aqueous cations (Berndt et al., 1989).

Future improvements in the application of laboratory dissolution data to natural systems will come not (only) from additional work on laboratory kinetics, but will also depend heavily on much more comprehensive studies of surface area distribution, evolution, and accessibility to attack by fluids in natural systems, and by improved understanding of thermodynamic properties of natural fluids. Only in this way will laboratory kinetic data contribute to solving environmental problems such as nuclear waste disposal and evaluating the impact of acid deposition. 

An analogy may be drawn between the phase behavior of weakly attractive monodisperse dispersions and that of conventional molecular systems provided coalescence and Ostwald ripening do not occur. The similarity arises from the common form of the pair potential, whose dominant feature in both cases is the presence of a shallow minimum. The equilibrium statistical mechanics of such systems have been extensively explored. As previously explained, the primary difficulty in predicting equilibrium phase behavior lies in the many-body interactions intrinsic to any condensed phase. Fortunately, the synthesis of several methods (integral equation approaches, perturbation theories, virial expansions, and computer simulations) now provides accurate predictions of thermodynamic properties and phase behavior of dense molecular fluids or colloidal fluids [1]. 

Finding Work of Compression with a Thermodynamic Chart Hydrogen sulfide is to be compressed from 100°F and atmospheric pressure to SOpsig. The isentropic efficiency is 0.70. A pressure-enthalpy chart is taken from Starling (Fluid Thermodynamic Properties for Light Petroleum Systems, Gulf, Houston, TX, 1973). The work and the complete thermodynamic conditions for the process will be found. 

In the case of continuous systems, for which the Mate changes from point to pointlfor example, a flow field of a viscous fluid), it is assumed that at every point, the equation of state is the same as for a homogeneous system and does not involve the gradients of the thermodynamic properties. Hence, such systems can only be studied with the aid of thermodynamics if local departures from equilibrium are small (near-equilihrium processes), i.c.. if the gradients of the thermodynamic properties are not too great. 

The (liquid 4- liquid) equilibria diagram for (cyclohexane + methanol) was taken from D. C. Jones and S. Amstell, The Critical Solution Temperature of the System Methyl Alcohol-Cyclohexane as a Means of Detecting and Estimating Water in Methyl Alcohol , J. Chem. Soc., 1930, 1316-1323 (1930). The G results were calculated from the (vapor 4- liquid) results of K. Strubl, V. Svoboda, R. Holub, and J. Pick, Liquid-Vapour Equilibrium. XIV. Isothermal Equilibrium and Calculation of Excess Functions in the Systems Methanol -Cyclohexane and Cyclohexane-Propanol , Collect. Czech. Chem. Commun., 35, 3004-3019 (1970). The results are from M. Dai and J.-P.Chao, Studies on Thermodynamic Properties of Binary Systems Containing Alcohols. II. Excess Enthalpies of C to C5 Normal Alcohols + 1,4-Dioxane , Fluid Phase Equilib., 23, 321-326 (1985). 

Chapters 17 and 18 use thermodynamics to describe solutions, with nonelectrolyte solutions described in Chapter 17 and electrolyte solutions described in Chapter 18. Chapter 17 focuses on the excess thermodynamic properties, with the properties of the ideal and regular solution compared with the real solution. Deviations from ideal solution behavior are correlated with the type of interactions in the liquid mixture, and extensions are made to systems with (liquid + liquid) phase equilibrium, and (fluid -I- fluid) phase equilibrium when the mixture involves supercritical fluids. 

Surface effects are negligible in many cases. However, when the surface-to-volume ratio of the system is large, surface effects may become appreciable. Moreover, there are phenomena associated with surfaces that are important in themselves. Only an introduction to the thermodynamics of surfaces can be given here, and the discussion is limited to fluid phases and the surfaces between such phases. Thus, consideration of solid-fluid interfaces are omitted, although the basic equations that are developed are applicable to such interfaces provided that the specific face of the crystal is designated. Also, the thermodynamic properties of films are omitted. 

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