Supercritical liquidgas boundaries

Supercritical liquidgas boundaries are lines in the p

T diagram that delimit more liquid-like and more gas-like
states of a supercritical uid. They comprise the Fisher
Widom line, the Widom line, and the Frenkel line.

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 3kB (where kB is the
Boltzmann constant). The contribution to the heat capacity due to the potential part of transverse excitations
is 1kB . Therefore at the Frenkel line, where transverse
excitations vanish, the isochoric heat capacity per particle should be cV = 2kB , a direct prediction from the
phonon theory of liquid thermodynamics.[4][5][6]

Overview

Anisimov et al. (2004),[7] without referring to Frenkel,

Fisher or Widom, reviewed thermodynamic derivatives
(specic heat, expansion coecient, compressibility) and
transport coecients (viscosity, speed of sound) in supercritical water, and found pronounced extrema as function
of pressure up to 100 K above T .

2 References
[1] Michael Fisher, Benjamin Widom: Decay of Correlations
in Linear Systems, J. Chem. Phys. 50, 3756 (1969)

supercritical gas-liquid boundaries in PT-diagram

[2] Boston University Research Briefs (2003), http://www.

bu.edu/phpbin/researchbriefs/display.php?id=659

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, dierent criteria still allow to distinguish liquid-like and more
gas-like states of a supercritical uid. These criteria result in dierent 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 rst or second order
phase transitions, but to weaker singularities.

[3] Brazhkin et al., Phys. Rev. E 85, 031203 (2012).

[4] D. Bolmatov, V. V. Brazhkin, and K. Trachenko The
phonon theory of liquid thermodynamics, Scientic Reports 2 421 (2012)
[5] Dima Bolmatov, V. V. Brazhkin, and K. Trachenko
Thermodynamic behaviour of supercritical matter, Scientic Reports 4 2331 (2013)
[6] Phonon theory sheds light on liquid thermodynamics,
PhysicsWorld, 2012

The FisherWidom line[1] is the boundary between

monotonic and oscillating asymptotics of the pair correlation function G(r) .

[7] Anisimov, Sengers, Levelt Sengers: Near-critical behavior of acquous systems. Chapter 2 in Aqueous System at
Elevated Temperatures and Pressures, Palmer et al. eds.,
Elsevier (2004).

The Widom line is a generalization thereof, apparently

introduced by H. Eugene Stanley.[2]
The Frenkel line is a boundary between rigid and nonrigid uids characterized by the onset of transverse
sound modes.[3]
1

3 TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

Text and image sources, contributors, and licenses

3.1

Text

Supercritical liquidgas boundaries Source: https://en.wikipedia.org/wiki/Supercritical_liquid%E2%80%93gas_boundaries?oldid=

752834933 Contributors: Bgwhite, RussBot, JorisvS, David Eppstein, Arjayay, Yobot, Omnipaedista, J6w5, Tom.Reding, Cnwilliams,
Bamyers99, Wgolf, Julia Abril, 115ash, WordSeventeen, Purgy Purgatorio and Davidcohen63

3.2

Images

File:PT-FrenkelFisherWidomSchematic.png
Source:
https://upload.wikimedia.org/wikipedia/commons/2/24/
PT-FrenkelFisherWidomSchematic.png License: CC BY-SA 4.0 Contributors: Own work Original artist: Purgy Purgatorio

3.3

Content license

Creative Commons Attribution-Share Alike 3.0