Heat capacity anomalies along the critical isotherm in fluid-fluid phase transitions

Journal of Chemical Physics

Volumn 132, Issue 15, 2010, Pages

  Losada Ṕrez, Patricia ^a,b   Ṕrez Sánchez, Germán ^a   Troncoso, Jacobo ^a   Cerdeiria, Claudio A ^a  

^a UNIVERSITY OF VIGO   (Spain)

^b UNIVERSITY OF LEUVEN   (Belgium)

Author keywords

[No Author keywords available]

Indexed keywords

CONSTANT COMPOSITION; CRITICAL AMPLITUDES; CRITICAL REGION; EXPERIMENTAL UNCERTAINTY; EXPLICIT EXPRESSIONS; FLUID CRITICALITY; FLUID-FLUID PHASE TRANSITION; HEAT CAPACITIES; ISOBARIC HEAT CAPACITY; ISOBUTANOL; ISOCHORIC HEAT CAPACITY; LINEAR TERMS; LIQUID-LIQUID CRITICAL POINT; MOLE FRACTION; NITROMETHANE; PURE FLUIDS; SCALING FUNCTIONS; TOPOLOGICAL FEATURES;

DATA VISUALIZATION; EQUATIONS OF STATE; LIQUIDS; PHASE EQUILIBRIA; SPECIFIC HEAT; TOLUENE; VISUALIZATION;

BINARY MIXTURES;

EID: 77951671112     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.3374819     Document Type: Article

References (32)

1. A summary of numerical values of universal quantities for the 3D-Ising class has been recently published: M. Barmatz, I. Hahn, J. A. Lipa, and R. V. Duncan, Rev. Mod. Phys. RMPHAT 0034-6861 79, 1 (2007). 10.1103/RevModPhys.79.1 (Pubitemid 46135266)
2. A. Hankey and H. E. Stanley, Phys. Rev. B PRBMDO 0163-1829 6, 3515 (1972). 10.1103/PhysRevB.6.3515
3. A path of constant pressure will be considered for binary mixtures.
4. M. E. Fisher and G. Orkoulas, Phys. Rev. Lett. PRLTAO 0031-9007 85, 696 (2000). 10.1103/PhysRevLett.85.696
5. Y. C. Kim, M. E. Fisher, and G. Orkoulas, Phys. Rev. E PLEEE8 1063-651X 67, 061506 (2003). 10.1103/PhysRevE.67.061506
6. C. A. Cerdeiria, M. A. Anisimov, and J. V. Sengers, Chem. Phys. Lett. CHPLBC 0009-2614 424, 414 (2006). 10.1016/j.cplett.2006.04.044 (Pubitemid 43850445)
7. M. A. Anisimov and J. T. Wang, Phys. Rev. Lett. PRLTAO 0031-9007 97, 025703 (2006). 10.1103/PhysRevLett.97.025703 (Pubitemid 44464332)
8. J. T. Wang and M. A. Anisimov, Phys. Rev. E PLEEE8 1063-651X 75, 051107 (2007). 10.1103/PhysRevE.75.051107 (Pubitemid 47013690)
9. J. T. Wang, C. A. Cerdeiria, M. A. Anisimov, and J. V. Sengers, Phys. Rev. E PLEEE8 1063-651X 77, 031127 (2008). 10.1103/PhysRevE.77.031127 (Pubitemid 351465358)
10. H. Behnejad, J. V. Sengers, and M. A. Anisimov, in Applied Thermodynamics, edited by, A. H. Goodwin, J. V. Sengers, and, C. J. Peters, IUPAC Chemical Data Series No. XX (Royal Society of Chemistry, London, in press), Chap..
11. G. Ṕrez-Sánchez, P. Losada-Ṕrez, C. A. Cerdeiria, J. V. Sengers, and M. A. Anisimov, J. Chem. Phys. JCPSA6 0021-9606 132, 154502 (2010). 10.1063/1.3378626
12. V (ρ,T) studies by the group of I. M. Abdulagatov have appeared during the last 15 years.
13. We refer to fields and densities in the sense explained by R. B. Griffiths and J. C. Wheeler, Phys. Rev. A PLRAAN 1050-2947 2, 1047 (1970). 10.1103/PhysRevA.2.1047
14. Such extra variables have been referred to as nonordering fields: see M. E. Fisher and M. C. Barbosa, Phys. Rev. B PRBMDO 0163-1829 43, 11177 (1991). 10.1103/PhysRevB.43.11177
15. M. A. Anisimov, E. E. Gorodetskii, V. D. Kulikov, and J. V. Sengers, Phys. Rev. E PLEEE8 1063-651X 51, 1199 (1995). 10.1103/PhysRevE.51.1199
16. M. E. Fisher and Y. C. Kim, J. Chem. Phys. JCPSA6 0021-9606 117, 779 (2002). 10.1063/1.1481381
17. Rather lengthy expressions for many critical amplitudes are not shown here. They will be provided to the interested reader upon request.
18. 2 is lesser than 1 as a consequence of thermodynamic convexity: C. A. Cerdeiria, G. Orkoulas, and M. E. Fisher (unpublished).
19. See, e.g., J. Rehr and N. D. Mermin, Phys. Rev. A PLRAAN 1050-2947 8, 472 (1973) 10.1103/PhysRevA.8.472;
20. M. Ley-Koo and M. S. Green, Phys. Rev. A PLRAAN 1050-2947 23, 2650 (1981). 10.1103/PhysRevA.23.2650
21. C. N. Yang and C. P. Yang, Phys. Rev. Lett. PRLTAO 0031-9007 13, 303 (1964). 10.1103/PhysRevLett.13.303
22. G. Ṕrez-Sánchez, P. Losada-Ṕrez, C. A. Cerdeiria, and J. Thoen (unpublished).
23. In order to make contact with theory the heat capacity per unit volume should best be considered; however, no problems arise with analyzing data per mole whenever higher-order singularities are disregarded, which, as we shall see, is actually the case.
24. N. G. Polikhronidi, I. M. Abdulagatov, J. W. Magee, and R. G. Batyrova, J. Chem. Eng. Data JCEAAX 0021-9568 46, 1064 (2001). 10.1021/je000269y (Pubitemid 32903194)
25. As shown recently [J. Troncoso, C. A. Cerdeiria, P. Losada-Ṕrez, E. Carballo, and L. Romaní, Fluid Phase Equilib. FPEQDT 0378-3812 280, 144 (2009)], c p,x E is more sensitive to critical fluctuations than cp,x since the background carries less weight. 10.1016/j.fluid.2009.03.023
26. It is well known that liquid-liquid phase transition temperatures are quite (sometimes dramatically) sensitive to impurities.
27. C. A. Cerdeiria, J. A. Míguez, E. Carballo, C. A. Tovar, E. de la Puente, and L. Romaní, Thermochim. Acta THACAS 0040-6031 45, 954 (2000).
28. C. A. Cerdeiria, J. Troncoso, E. Carballo, and L. Romaní, Phys. Rev. E PLEEE8 1063-651X 66, 031507 (2002). 10.1103/PhysRevE.66.031507 (Pubitemid 40606384)
29. J. Troncoso, D. González-Salgado, C. A. Cerdeiria, E. Carballo, and L. Romaní, Phys. Rev. E PLEEE8 1063-651X 71, 021503 (2005). 10.1103/PhysRevE.71.021503 (Pubitemid 40606981)
30. M. Souto-Caride, J. Troncoso, J. Peleteiro, E. Carballo, and L. Romaní, Chem. Phys. CMPHC2 0301-0104 324, 483 (2006). 10.1016/j.chemphys.2005.11.009
31. P. Losada-Ṕrez, G. Ṕrez-Sánchez, C. A. Cerdeiria, J. Troncoso, and L. Romaní, J. Chem. Phys. JCPSA6 0021-9606 130, 044506 (2009). 10.1063/1.3054351
32. See supplementary material at http://dx.doi.org/10.1063/1.3374819 E-JCPSA6-132-023013 for numerical values of experimental data.