Supercritical liquid–gas boundaries

Supercritical liquid–gas boundaries are lines in the p–T diagram that delimit more liquid-like and more gas-like states of a supercritical fluid. They comprise the Fisher–Widom line, the Widom line, and the Frenkel line.

Overview
supercritical gas-liquid boundaries in PT-diagram (“liquid” and “gas” labels should switch positions)

According to textbook knowledge, it is possible to transform a liquid continuously into a gas, without undergoing a phase transition, by heating and compressing strongly enough to go around the critical point. However, different criteria still allow to distinguish liquid-like and more gas-like states of a supercritical fluid. These criteria result in different boundaries in the pT plane. These lines emanate either from the critical point, or from the liquid–vapor boundary (boiling curve) somewhat below the critical point. They do not correspond to first or second order phase transitions, but to weaker singularities.

The Fisher–Widom line[1] is the boundary between monotonic and oscillating asymptotics of the pair correlation function .

The Widom line is a generalization thereof, apparently so named by H. Eugene Stanley.[2] However, it was first measured experimentally in 1956 by Jones and Walker[3], and subsequently named the 'hypercritical line' by Bernal in 1964[4], who suggested a structural interpretation. The Frenkel line is a boundary between "rigid" and "non-rigid" fluids characterized by the onset of transverse sound modes.[5]

One of the above mentioned criteria is based on the velocity autocorrelation function (vacf): below the Frenkel line the vacf demonstrates oscillatory behaviour, while above it the vacf monotonically decays to zero. The second criterion is based on the fact that at moderate temperatures liquids can sustain transverse excitations, which disappear upon heating. One further criterion is based on isochoric heat capacity measurements. The isochoric heat capacity per particle of a monatomic liquid near to the melting line is close to (where is the Boltzmann constant). The contribution to the heat capacity due to the potential part of transverse excitations is . Therefore at the Frenkel line, where transverse excitations vanish, the isochoric heat capacity per particle should be , a direct prediction from the phonon theory of liquid thermodynamics.[6][7][8]

Anisimov et al. (2004),[9] without referring to Frenkel, Fisher or Widom, reviewed thermodynamic derivatives (specific heat, expansion coefficient, compressibility) and transport coefficients (viscosity, speed of sound) in supercritical water, and found pronounced extrema as function of pressure up to 100 K above Tc.

References
  1. Fisher, Michael E.; Widom, B. (1969). "Decay of Correlations in Linear Systems". The Journal of Chemical Physics. AIP Publishing. 50 (9): 3756–3772. doi:10.1063/1.1671624. ISSN 0021-9606.
  2. Boston University Research Briefs (2003), http://www.bu.edu/phpbin/researchbriefs/display.php?id=659
  3. Jones; Walker (1956). "Specific Heats of Fluid Argon near the Critical Point". Proc. Phys. Soc. B. 69 (12): 1348–1350. doi:10.1088/0370-1301/69/12/125.
  4. Bernal, J.D. (1964-07-28). "The Bakerian Lecture, 1962 The structure of liquids". Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences. The Royal Society. 280 (1382): 299–322. doi:10.1098/rspa.1964.0147. ISSN 2053-9169.
  5. Brazhkin, V. V.; Fomin, Yu. D.; Lyapin, A. G.; Ryzhov, V. N.; Trachenko, K. (2012-03-30). "Two liquid states of matter: A dynamic line on a phase diagram". Physical Review E. American Physical Society (APS). 85 (3): 031203. arXiv:1104.3414. doi:10.1103/physreve.85.031203. ISSN 1539-3755.
  6. Bolmatov, D.; Brazhkin, V. V.; Trachenko, K. (2012-05-24). "The phonon theory of liquid thermodynamics". Scientific Reports. Springer Science and Business Media LLC. 2 (1): 421. doi:10.1038/srep00421. ISSN 2045-2322.
  7. Bolmatov, Dima; Brazhkin, V. V.; Trachenko, K. (2013-08-16). "Thermodynamic behaviour of supercritical matter". Nature Communications. Springer Science and Business Media LLC. 4 (1): 2331. doi:10.1038/ncomms3331. ISSN 2041-1723.
  8. "Phonon theory sheds light on liquid thermodynamics", PhysicsWorld, 2012
  9. Anisimov, Sengers, Levelt Sengers: Near-critical behavior of aqueous systems. Chapter 2 in Aqueous System at Elevated Temperatures and Pressures, Palmer et al. eds., Elsevier (2004).
  • Simeoni, G. G.; Bryk, T.; Gorelli, F. A.; Krisch, M.; Ruocco, G.; Santoro, M.; Scopigno, T. (2010-06-06). "The Widom line as the crossover between liquid-like and gas-like behaviour in supercritical fluids". Nature Physics. Springer Science and Business Media LLC. 6 (7): 503–507. doi:10.1038/nphys1683. ISSN 1745-2473.
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