Most accurate equation of state

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Discussion Overview

The discussion revolves around identifying the most accurate equation of state in physical chemistry, particularly one that maintains accuracy across a wide range of pressures and temperatures while minimizing the number of parameters. Participants explore various equations of state, including the van der Waals equation, and their applicability in different phases of matter.

Discussion Character

  • Debate/contested
  • Technical explanation
  • Conceptual clarification

Main Points Raised

  • One participant suggests the van der Waals equation, particularly with a Maxwell construction, as a candidate for the most accurate equation of state, but notes its limitations near the critical point.
  • Another participant questions the existence of a significantly more accurate equation of state derived from pure theory compared to the van der Waals equation, arguing that introducing more parameters may complicate the model without improving accuracy.
  • It is mentioned that various fitted curves are commonly used in practical applications, as they can provide better empirical results than more complex theoretical models.
  • A participant highlights that the van der Waals equation performs poorly in the liquid phase and is not applicable to solids, which require different equations of state depending on their properties (insulator, semiconductor, metal).
  • Advanced methods, such as Greensfunction methods, are noted as sophisticated approaches to derive equations of state, alongside empirical engineering methods.
  • Concerns are raised about the van der Waals equation's inadequacy in the critical region, with special techniques developed in the 1970s to address this issue.

Areas of Agreement / Disagreement

Participants express differing views on the accuracy and applicability of the van der Waals equation compared to other equations of state. There is no consensus on a singular "most accurate" equation, and the discussion reflects multiple competing perspectives on the topic.

Contextual Notes

The discussion highlights limitations in the applicability of the van der Waals equation, particularly in different phases of matter and near critical points. It also notes the complexity introduced by additional parameters in theoretical models.

hawkingfan
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I've come across many equations of state in physical chemistry. (only a fraction of those that actually exist) Does anybody have any idea of the most accurate one to date. By accurate, I mean that it is accurate for the largest ranges of pressure and temperature by taking into account the least amount of parameters. Right now, the most accurate one that I can think of is the van der Waals equation when using a Maxwell construction. (as long as it isn't too close to the critical point) Are there any better ones as of 2010.
 
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Almost a week and no answers. I guess that nobody knows the exact answer. I'll rephrase this. What's the most accurate equation of state that you know of? It does not have to be the most accurate one out there. Please give a pressure and temperature range at which it's applicable. Thanks for your answers if you have any.
 
As far as I know, there's no equation of state derived from pure theory that's significantly more accurate than the van der Waals one.

Basically, there wouldn't be much point in attempting to develop such an equation. You could introduce more parameters to better describe molecular geometry, the various intermolecular potentials, dipole moment, polarizability, etc. But the end result would be an equation that would be both more complicated and less accurate than what you'd get from just empirically fitting some curve using the same number of parameters.

So from the practical/engineering standpoint, that's what they use, various fitted curves. From the theoretical standpoint, we're more interested in studying the details behind phase changes and how the (non-idealized) bulk properties emerge from to the microscopic ones (something which is still not well known, even for stuff like water). Nobody's looking for a simple general "formula", because we know there's not going to be one.
 
The van der Waals equation is an equation of state which describes only liquids and gasses and does already a rather bad job in the liquid phase. For solids there are completely different equations of state, which also depend on whether you want to describe an insulator, a semiconductor or a metal. There are both highly sofisticated ab initio methods to derive equations of state, e.g. Greensfunction methods and more empirical engineering approaches. The van der Waals equation also describes very badly the region around the critical point and special techniques for this region have been developed in the 1970's.
 

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