Critical points: Difference between revisions

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[[Image:press_temp.png|thumb|right]]
Critical points are singularities in the [[partition function]].
The '''critical point''', discovered in 1822 by Charles Cagniard de la Tour <ref>Charles Cagniard de la Tour "Exposé de quelques résultats obtenu par l'action combinée de la chaleur et de la compression sur certains liquides, tels que l'eau, l'alcool, l'éther sulfurique et l'essence de pétrole rectifiée", Annales de chimie et de physique '''21''' pp. 127-132 (1822)</ref><ref>[http://dx.doi.org/10.1590/S1806-11172009000200015 Bertrand Berche, Malte Henkel, and Ralph Kenna "Critical phenomena: 150 years since Cagniard de la Tour", Revista Brasileira de Ensino de Física '''31''' pp.2602.1-2602.4 (2009)] (in English [http://arxiv.org/abs/0905.1886v1 arXiv:0905.1886v1])</ref> , is a point found at the end of the liquid-vapour coexistence curve (the red point shown on the [[pressure-temperature]] plot on the right). At this point the [[temperature]] is known as the ''critical temperature'' <math>(T_c)</math>
In the critical point vicinity  (Ref. 1 Eq. 17a)
and the [[pressure]] is known as the ''critical pressure'' <math>(P_c)</math>.
For an interesting discourse on the "discovery" of the liquid-vapour critical point, the  Bakerian Lecture of [[Thomas Andrews]]
makes good reading <ref>[http://links.jstor.org/sici?sici=0261-0523%281869%29159%3C575%3ATBLOTC%3E2.0.CO%3B2-0 Thomas Andrews "The Bakerian Lecture: On the Continuity of the Gaseous and Liquid States of Matter", Philosophical Transactions of the Royal Society of London '''159''' pp. 575-590 (1869)]</ref>. Critical points are singularities in the [[partition function]].
In the critical point vicinity  (Ref. <ref>[http://dx.doi.org/10.1080/00268978300102111 G. A. Martynov; G. N. Sarkisov "Exact equations and the theory of liquids. V", Molecular Physics '''49''' pp. 1495-1504 (1983)]</ref> Eq. 17a)


:<math> \left.\frac{\partial P}{\partial n}\right\vert_{T}  \simeq 0</math>  
:<math> \left.\frac{\partial P}{\partial n}\right\vert_{T}  \simeq 0</math>  
Line 9: Line 12:
:<math>n \int_0^{\infty} c(r) ~4 \pi r^2 ~{\rm d}r \simeq  1</math>
:<math>n \int_0^{\infty} c(r) ~4 \pi r^2 ~{\rm d}r \simeq  1</math>


For a review of the critical region see the work of Michael E. Fisher (Ref. 2).
For a review of the critical region see the work of Michael E. Fisher <ref>[http://dx.doi.org/10.1063/1.1704197  Michael E. Fisher "Correlation Functions and the Critical Region of Simple Fluids", Journal of Mathematical Physics '''5''' pp. 944-962 (1964)]</ref>
 
<blockquote>
... Turning now to the question of specific heats, it has long been known
"... Turning now to the question of specific heats, it has long been known
that real gases exhibit a large ``anomalous" specific-heat maximum
that real gases exhibit a large ``anomalous" specific-heat maximum
above <math>T_c</math> which lies near the critical isochore and which is not expected on classical theory..." (Ref. 3)
above <math>T_c</math> which lies near the critical isochore and which is not expected on classical theory..."
 
</blockquote>
also
also
 
<blockquote>
... measurements (Ref 4) of <math>C_V(T)</math> for argon along the critical isochore suggest strongly that
"... measurements (Ref. <ref>[http://dx.doi.org/10.1016/S0031-8914(58)80093-2  A. Michels, J.M. Levelt and G.J. Wolkers "Thermodynamic properties of argon at temperatures between 0°C and −140°C and at densities up to 640 amagat (pressures up to 1050 atm.)", Physica '''24''' pp. 769-794 (1958)]</ref> ) of <math>C_V(T)</math> for argon along the critical isochore suggest strongly that
<math>C_V(T) \rightarrow \infty ~{\rm as} ~ T  \rightarrow  T_c \pm</math>. Such a result is again inconsistent with classical theory."
<math>C_V(T) \rightarrow \infty ~{\rm as} ~ T  \rightarrow  T_c \pm</math>. Such a result is again inconsistent with classical theory."
 
</blockquote>
Thus in the vicinity of the liquid-vapour critical point, both the [[Compressibility | isothermal compressibility]]  
Thus in the vicinity of the liquid-vapour critical point, both the [[Compressibility | isothermal compressibility]]  
and the [[heat capacity]] at constant pressure diverge to infinity.
and the [[heat capacity]] at constant pressure diverge to infinity.
==Liquid-liquid critical point==
==Solid-liquid critical point==
It is widely held that there is no solid-liquid critical point. The reasoning behind this was given on the grounds of symmetry by Landau and Lifshitz
<ref>L. D. Landau and E. M. Lifshitz, "Statistical Physics" (Course of Theoretical Physics, Volume 5) 3rd Edition Part 1, Chapter XIV, Pergamon Press (1980) &sect; 83 p. 258</ref>. However, recent work using the [[Z1 and Z2 potentials |Z2 potential]] suggests that this may not be the last word on the subject.
<ref>[http://dx.doi.org/10.1063/1.3213616 Måns Elenius and Mikhail Dzugutov "Evidence for a liquid-solid critical point in a simple monatomic system", Journal of Chemical Physics 131, 104502 (2009)]</ref>.
==Tricritical points==
*[http://dx.doi.org/10.1103/PhysRevLett.24.715  Robert B. Griffiths "Thermodynamics Near the Two-Fluid Critical Mixing Point in He<sup>3</sup> - He<sup>4</sup>", Physical Review Letters '''24'''  715-717 (1970)]
*[http://dx.doi.org/10.1063/1.451007 Lech Longa "On the tricritical point of the nematic–smectic A phase transition in liquid crystals", Journal of Chemical Physics '''85''' pp. 2974-2985 (1986)]
==Critical exponents==
==Critical exponents==
[[Heat capacity |Specific heat]], ''C''
:''Main article: [[Critical exponents]]''
 
==Yang-Yang anomaly==
:<math>\left. C\right.=C_0 \epsilon^{-\alpha}</math>
:''Main article: [[Yang-Yang anomaly]]''
 
==See also==
Magnetic order parameter, ''m'',
*[[Binder cumulant]]
 
*[[Law of corresponding states]]
:<math>\left. m\right. = m_0 \epsilon^\beta</math>
==References==
 
<references/>
[[Susceptibility]]  
'''Related reading'''
* M. I. Bagatskii and A. V. Voronel and B. G. Gusak "", Journal of Experimental and Theoretical Physics '''16''' pp. 517- (1963)
* [http://dx.doi.org/10.1103/PhysRevA.2.1047 Robert B. Griffiths and John C. Wheeler "Critical Points in Multicomponent Systems", Physical Review A '''2''' 1047 - 1064 (1970)]
* [http://dx.doi.org/10.1103/RevModPhys.46.597 Michael E. Fisher "The renormalization group in the theory of critical behavior", Reviews of Modern Physics '''46''' pp. 597 - 616 (1974)]
* [http://dx.doi.org/10.1146/annurev.pc.37.100186.001201  J. V. Sengers and  J. M. H. Levelt Sengers "Thermodynamic Behavior of Fluids Near the Critical Point", Annual Review of Physical Chemistry '''37''' pp. 189-222 (1986)]
* [http://dx.doi.org/10.1103/PhysRevLett.93.015701  Kamakshi Jagannathan and Arun Yethiraj "Molecular Dynamics Simulations of a Fluid near Its Critical Point", Physical Review Letters '''93''' 015701 (2004)]
*[http://dx.doi.org/10.1080/00268976.2010.495734 Kurt Binder "Computer simulations of critical phenomena and phase behaviour of fluids", Molecular Physics '''108''' pp. 1797-1815 (2010)]
;Books
* H. Eugene Stanley "Introduction to Phase Transitions and Critical Phenomena", Oxford University Press (1971) ISBN 9780195053166
* Cyril Domb "The Critical Point: A Historical Introduction To The Modern Theory Of Critical Phenomena", Taylor and Francis (1996) ISBN 9780748404353


:<math>\left. \chi \right. = \chi_0 \epsilon^{-\gamma}</math>
Correlation length
:<math>\left. \xi \right.= \xi_0 \epsilon^{-\nu}</math>
where <math>\epsilon</math> is the reduced distance from the critical [[temperature]], i.e.
:<math>\epsilon = \left| 1 -\frac{T}{T_c}\right|</math>
Note that this implies a certain symmetry when the critical point is approached from either 'above' or 'below', which is not  necessarily the case.
Rushbrooke equality
:<math>\alpha + 2\beta + \gamma =2</math>
===Gamma divergence===
When approaching the critical point along the critical isochore (<math>T > T_c</math>) the divergence is of the form
:<math>\left. \right. C_p \sim \kappa_T \sim (T-T_c)^{-\gamma} \sim (p-p_c)^{-\gamma}</math>
where <math>\gamma</math> is 1.0 for the [[Van der Waals equation of state]], and is usually 1.2 to 1.3.
===Epsilon divergence===
When approaching the critical point along the critical isotherm the divergence is of the form
:<math>\left. \right. \kappa_T \sim  (p-p_c)^{-\epsilon}</math>
where <math>\epsilon</math> is 2/3 for the [[Van der Waals equation of state]], and is usually 0.75 to 0.8.
==References==
#[http://dx.doi.org/10.1080/00268978300102111 G. A. Martynov; G. N. Sarkisov "Exact equations and the theory of liquids. V", Molecular Physics '''49''' pp. 1495-1504 (1983)]
#[http://dx.doi.org/10.1063/1.1704197  Michael E. Fisher "Correlation Functions and the Critical Region of Simple Fluids", Journal of Mathematical Physics '''5''' pp. 944-962 (1964)]
#[http://dx.doi.org/10.1016/S0031-8914(58)80093-2  A. Michels, J.M. Levelt and G.J. Wolkers "Thermodynamic properties of argon at temperatures between 0°C and −140°C and at densities up to 640 amagat (pressures up to 1050 atm.)", Physica '''24''' pp. 769-794 (1958)]
# M. I. Bagatskii and A. V. Voronel and B. G. Gusak "", Journal of Experimental and Theoretical Physics '''16''' pp. 517- (1963)
#[http://dx.doi.org/10.1103/PhysRevA.2.1047 Robert B. Griffiths and John C. Wheeler "Critical Points in Multicomponent Systems", Physical Review A '''2''' 1047 - 1064 (1970)]
#[http://dx.doi.org/10.1103/RevModPhys.46.597 Michael E. Fisher "The renormalization group in the theory of critical behavior", Reviews of Modern Physics '''46''' pp. 597 - 616 (1974)]
#[http://dx.doi.org/10.1146/annurev.pc.37.100186.001201  J. V. Sengers and  J. M. H. Levelt Sengers "Thermodynamic Behavior of Fluids Near the Critical Point", Annual Review of Physical Chemistry '''37''' pp. 189-222 (1986)]
[[category: statistical mechanics]]
[[category: statistical mechanics]]
[[category:classical thermodynamics]]
[[category:classical thermodynamics]]

Latest revision as of 15:32, 4 January 2012

The critical point, discovered in 1822 by Charles Cagniard de la Tour [1][2] , is a point found at the end of the liquid-vapour coexistence curve (the red point shown on the pressure-temperature plot on the right). At this point the temperature is known as the critical temperature and the pressure is known as the critical pressure . For an interesting discourse on the "discovery" of the liquid-vapour critical point, the Bakerian Lecture of Thomas Andrews makes good reading [3]. Critical points are singularities in the partition function. In the critical point vicinity (Ref. [4] Eq. 17a)

and

For a review of the critical region see the work of Michael E. Fisher [5]

"... Turning now to the question of specific heats, it has long been known that real gases exhibit a large ``anomalous" specific-heat maximum above which lies near the critical isochore and which is not expected on classical theory..."

also

"... measurements (Ref. [6] ) of for argon along the critical isochore suggest strongly that . Such a result is again inconsistent with classical theory."

Thus in the vicinity of the liquid-vapour critical point, both the isothermal compressibility and the heat capacity at constant pressure diverge to infinity.

Liquid-liquid critical point[edit]

Solid-liquid critical point[edit]

It is widely held that there is no solid-liquid critical point. The reasoning behind this was given on the grounds of symmetry by Landau and Lifshitz [7]. However, recent work using the Z2 potential suggests that this may not be the last word on the subject. [8].

Tricritical points[edit]

Critical exponents[edit]

Main article: Critical exponents

Yang-Yang anomaly[edit]

Main article: Yang-Yang anomaly

See also[edit]

References[edit]

Related reading

Books
  • H. Eugene Stanley "Introduction to Phase Transitions and Critical Phenomena", Oxford University Press (1971) ISBN 9780195053166
  • Cyril Domb "The Critical Point: A Historical Introduction To The Modern Theory Of Critical Phenomena", Taylor and Francis (1996) ISBN 9780748404353