Absolute Internal Energy of the Real Gas

The internal energy U of the real, neutral-gas particles of total mass M in the volume V can have positive and negative values, whose regions are identified in the state chart of the gas. Depending on the relations among gas temperature T, pressure p and mass-specific volume v=V/M, the mass exists as a uniform gas of freely-moving particles having positive values U or as more or less structured matter with negative values U. In the regions U>0?above the critical point [Tc , pc , vc] it holds that p(T,v)>pc and v>vc, and below the critical point it holds that p(T,v)c and v>vv , where vv is the mass-specific volume of saturated vapor. In the adjacent regions with negative internal energy values Uc is the line of equal positive and negative energy contributions and thus represents a line of vanishing internal energy ?U=0. At this level along the critical isochor the ever present microscopic fluctuations in energy and density become macroscopic fluctuations as the pressure decreases on approaching the critical point;these are to be observed in experiments on the critical opalescence. Crossing the isochor vc from U>0 to UΔU>0 happens without any discontinuity. The saturation line vv also separates the regions between U>0 and U , but does not represent a line U=0. The internal-energy values of saturated vapor Uv and condensate Ui can be determined absolutely as functions of vapor pressure p and densities (M/V)v and (M/V)i , repectively, yielding the results Uiv, U=Ui+Uvc and U=Ui=Uv=0 at the critical point. Crossing the line Vv from U=Uv>0 to U=Uv+UiΔU=-Ui>0 to be removed from the particle system. The thermodynamic and quantum-mechanical formulations of the internal energy of a particle system only agree if both the macroscopic and microscopic energy scales have the same absolute energy reference value 0. Arguments for the energy reference value in the state of transition from bound to freely- moving particles in macroscopic classical and microscopic quantum particle systems are discussed.

Thermodynamic Equilibrium of the Saturated Fluid with a Free Surface Area and the Internal Energy as a Function of the Phase-Specific Volumes and Vapor Pressure

This study is concerned with describing the thermodynamic equilibrium of the saturated fluid with and without a free surface area A. Discussion of the role of A as system variable of the interface phase and an estimate of the ratio of the respective free energies of systems with and without A show that the system variables given by Gibbs suffice to describe the volumetric properties of the fluid. The well-known Gibbsian expressions for the internal energies of the two-phase fluid, namely for the vapor and for the condensate (liquid or solid), only differ with respect to the phase-specific volumes and . The saturation temperature T, vapor presssure p, and chemical potential are intensive parameters, each of which has the same value everywhere within the fluid, and hence are phase-independent quantities. If one succeeds in representing as a function of and , then the internal energies can also be described by expressions that only differ from one another with respect to their dependence on and . Here it is shown that can be uniquely expressed by the volume function . Therefore, the internal energies can be represented explicitly as functions of the vapor pressure and volumes of the saturated vapor and condensate and are absolutely determined. The hitherto existing problem of applied thermodynamics, calculating the internal energy from the measurable quantities T, p, , and , is thus solved. The same method applies to the calculation of the entropy, chemical potential, and heat capacity.

The Dominant Role of the Chemical Potential for Driving Currents in Oceans and Air

Applying the thermodynamic zeros of the entropy ?and internal energy ?of the gas mass ?in the volume ?yields the numerically unique relation between these quantities, thus allowing calculation of the chemical potential in the gas fields of temperature ?and pressure , viz. . A difference in chemical potential provides a force for freely moving matter flow. Since ?is intrinsically a negative function, decreasing as the temperature increases, natural flow processes are initiated by high ?values in cold regions directed to low <v:shape id="_x0000_i1034" type="#

Thermodynamic Fit Functions of the Two-Phase Fluid and Critical Exponents

Two-phase fluid properties such as entropy, internal energy, and heat capacity are given by thermodynamically defined fit functions. Each fit function is expressed as a temperature function in terms of a power series expansion about the critical point. The leading term with the critical exponent dominates the temperature variation between the critical and triple points. With β being introduced as the critical exponent for the difference between liquid and vapor densities, it is shown that the critical exponent of each fit function depends (if at all) on β. In particular, the critical exponent of the reciprocal heat capacity c﹣1 is α=1-2β and those of the entropy s and internal energy u are?2β, while that of the reciprocal isothermal compressibility?κ﹣1T is γ=1. It is thus found that in the case of the two-phase fluid the Rushbrooke equation conjectured α +?2β + γ=2 combines the scaling laws resulting from the two relations c=du/dT and?κT=dlnρ/dp. In the context with c, the second temperature derivatives of the chemical potential μ and vapor pressure p are investigated. As the critical point is approached, ﹣d2μ/dT2 diverges as c, while?d2p/dT2 converges to a finite limit. This is explicitly pointed out for the two-phase fluid, water (with β=0.3155). The positive and almost vanishing internal energy of the one-phase fluid at temperatures above and close to the critical point causes conditions for large long-wavelength density fluctuations, which are observed as critical opalescence. For negative values of the internal energy, i.e. the two-phase fluid below the critical point, there are only microscopic density fluctuations. Similar critical phenomena occur when cooling a dilute gas to its Bose-Einstein condensate.

Absolute Reference Values of the Real Gas

With his publication in 1873 [1] J. W. Gibbs formulated the thermodynamic theory. It describes almost all macroscopically observed properties of matter and could also describe all phenomena if only the free energy U - ST were explicitly known numerically. The thermodynamic uniqueness of the free energy obviously depends on that of the internal energy U and the entropy S, which in both cases Gibbs had been unable to specify. This uncertainty, lasting more than 100 years, was not eliminated either by Nernst’s hypothesis S = 0 at T = 0. This was not achieved till the advent of additional proof of the thermodynamic relation U = 0 at T = Tc. It is noteworthy that from purely thermodynamic consideration of intensive and extensive quantities it is possible to derive both Gibbs’s formulations of entropy and internal energy and their now established absolute reference values. Further proofs of the vanishing value of the internal energy at the critical point emanate from the fact that in the case of the saturated fluid both the internal energy and its phase-specific components can be represented as functions of the evaporation energy. Combining the differential expressions in Gibbs’s equation for the internal energy, d(μ/T)/d(1/T) and d(p/T)/d(1/T), to a new variable d(μ/T)/d(p/T) leads to a volume equation with the lower limit vc as boundary condition. By means of a variable transformation one obtains a functional equation for the sum of two dimensionless variables, each of them being related to an identical form of local interaction forces between fluid particles, but the different particle densities in the vapor and liquid spaces produce different interaction effects. The same functional equation also appears in another context relating to the internal energy. The solution of this equation can be given in analytic form and has been published [2] [3]. Using the solutions emerging in different sets of problems, one can calculate absolutely the internal energy as a function of temperature-dependent, phase-specific volumes and vapor pressure.