Master crossover behavior of parachor correlations for one-component fluids

Abstract

The master asymptotic behavior of the usual parachor correlations, expressing surface tension sigma as a power law of the density difference rho(L)-rho(V) between coexisting liquid and vapor, is analyzed for a series of pure compounds close to their liquid-vapor critical point, using only four critical parameters (beta(c))-1 , alpha(c) , Z(c) , and Y(c) , for each fluid. This is accomplished by the scale dilatation method of the fluid variables where, in addition to the energy unit (beta(c))-1 and the length unit alpha(c) , the dimensionless numbers Z(c) and Y(c) are the characteristic scale factors of the ordering field along the critical isotherm and of the temperature field along the critical isochore, respectively. The scale dilatation method is then formally analogous to the basic system-dependent formulation of the renormalization theory. Accounting for the hyperscaling law delta-1/delta+1=eta-2/2d , we show that the Ising-like asymptotic value pi(a) of the parachor exponent is unequivocally linked to the critical exponents eta or delta by pi(a)/d-1=2/d-(2-eta)=delta+1/d (here d=3 is the space dimension). Such mixed hyperscaling laws combine either the exponent eta or the exponent delta , which characterizes bulk critical properties of d dimension along the critical isotherm or exactly at the critical point, with the parachor exponent pi(a) which characterizes interfacial properties of d-1 dimension in the nonhomogeneous domain. Then we show that the asymptotic (symmetric) power law [abstract; see text] is the two-dimensional critical equation of state of the liquid-gas interface between the two-phase system at constant total (critical) density rho(c) . This power law complements the asymptotic (antisymmetric) form [abstract; see text] of the three-dimensional critical equation of state for a fluid of density rho not equal to rho_(c) and pressure p not equal to p_(c) , maintained at constant (critical) temperature T=T_(c)} [mu_(rho)(mu_(rho,c)) is the specific (critical) chemical potential; p_(c) is the critical pressure; and T_(c) is the critical temperature]. We demonstrate the existence of the related universal amplitude combination [abstract; see text] = universal constant, constructed with the amplitudes D_(rho)(sigma) and D_(rho)(c) , separating then the respective contributions of each scale factor Y_(c) and Z_(c) , characteristic of each thermodynamic path, i.e., the critical isochore and the critical isotherm (or the critical point), respectively. The main consequences of these theoretical estimations are discussed in light of engineering applications and process simulations where parachor correlations constitute one of the most practical methods for estimating surface tension from density and capillary rise measurements.