Asymmetric fluid criticality. I. Scaling with pressure mixing

被引:214
作者
Kim, YC [1 ]
Fisher, ME [1 ]
Orkoulas, G [1 ]
机构
[1] Univ Maryland, Inst Phys Sci & Technol, College Pk, MD 20742 USA
来源
PHYSICAL REVIEW E | 2003年 / 67卷 / 06期
关键词
D O I
10.1103/PhysRevE.67.061506
中图分类号
O35 [流体力学]; O53 [等离子体物理学];
学科分类号
070204 ; 080103 ; 080704 ;
摘要
The thermodynamic behavior of a fluid near a vapor-liquid and, hence, asymmetric critical point is discussed within a general "complete" scaling theory incorporating pressure mixing in the nonlinear scaling fields as well as corrections to scaling. This theory allows for a Yang-Yang anomaly in which mu(sigma)(')(T), the second temperature derivative of the chemical potential along the phase boundary, diverges like the specific heat when T-->T-c; it also generates a leading singular term, parallel totparallel to(2beta), in the coexistence curve diameter, where tequivalent to(T-T-c)/T-c. The behavior of various special loci, such as the critical isochore, the critical isotherm, the k-inflection loci, on which chi((k))equivalent tochi(rho,T)/rho(k) (with chi=rho(2)k(B)TK(T)) and C(V)((k))equivalent toC(V)(rho,T)/rho(k) are maximal at fixed T, is carefully elucidated. These results are useful for analyzing simulations and experiments, since particular, nonuniversal values of k specify loci that approach the critical density most rapidly and reflect the pressure-mixing coefficient. Concrete illustrations are presented for the hard-core square-well fluid and for the restricted primitive model electrolyte. For comparison, a discussion of the classical (or Landau) theory is presented briefly and various interesting loci are determined explicitly and illustrated quantitatively for a van der Waals fluid.
引用
收藏
页码:21 / 061506
页数:21
相关论文
共 39 条
[1]  
[Anonymous], PROGR LIQUID PHYSICS
[2]  
BAGATSKI MI, 1963, SOV PHYS JETP-USSR, V16, P517
[3]  
BARBER MN, 1977, PHYS REP, V29, P1
[4]   SCALING FIELDS AND UNIVERSALITY OF THE LIQUID-GAS CRITICAL-POINT [J].
BRUCE, AD ;
WILDING, NB .
PHYSICAL REVIEW LETTERS, 1992, 68 (02) :193-196
[5]   PHASE TRANSITIONS IN ONE-DEMENSIONAL CLUSTER-INTERACTION FLUIDS .1B. CRITICAL BEHAVIOR [J].
FISHER, ME ;
FELDERHOF, BU .
ANNALS OF PHYSICS, 1970, 58 (01) :217-+
[6]   The Yang-Yang anomaly in fluid criticality: Experiment and scaling theory [J].
Fisher, ME ;
Orkoulas, G .
PHYSICAL REVIEW LETTERS, 2000, 85 (04) :696-699
[7]   Renormalization group theory: Its basis and formulation in statistical physics [J].
Fisher, ME .
REVIEWS OF MODERN PHYSICS, 1998, 70 (02) :653-681
[8]  
FISHER ME, 1983, LECT NOTES PHYS, V186, P1
[9]   THEORY OF EQUILIBRIUM CRITICAL PHENOMENA [J].
FISHER, ME .
REPORTS ON PROGRESS IN PHYSICS, 1967, 30 :615-+
[10]   Right and wrong near critical endpoints [J].
Fisher, ME ;
Kim, YC .
JOURNAL OF CHEMICAL PHYSICS, 2002, 117 (02) :779-787