Can a Solid Have Lower Free Energy than a Liquid at Low Packing Densities?

In summary, the conversation discusses the conditions for coexistence between a solid and a liquid in a mixture of hard spheres. The potential energy for a hard sphere system is given, and the packing fraction is defined as the amount of space occupied by the particles. The equations of state for the hard sphere fluid and solid are presented, and the free energy as a function of packing density is calculated. The resulting phase diagram shows that the free energy of the solid phase is lower than that of the liquid phase, even at low densities. The possibility of incorrect plots and the existence of materials without a liquid phase at a specific temperature are also mentioned.
  • #1
lol_nl
41
0
In a nutshell, I am trying to see how to derive the conditions of coexistence between a solid and a liquid from a phase diagram.

The situation is as follows:
Consider a mixture of hard spheres of diameter σ. The potential energy
for a hard sphere system is given by
[itex]\beta U(r) = 0 (r > \sigma)
[/itex]
[itex]
∞ (r ≤ \sigma)
[/itex]
The packing fraction (η) of the system is the amount of space occupied
by the particles.
The equation of state for the hard sphere fluid is approximately
[itex]
\frac{P_{liq}V}{Nk_{B}T}= \frac{1+ \eta + \eta^2 - \eta^3}{ (1 - \eta)^3 }
[/itex]

Another similar equation is given for [itex]P_{sol}[/itex], the pressure in the solid state.

By integration I managed to calculated the free energy as a function of the packing density, using given boundary conditions. This resulted in the following diagram:
http://imageshack.us/a/img843/7475/54419842.png

Here the free energy is plotted against the packing density. The red line corresponds to the solid phase and the blue line to the liquid phase.

In general I would think one could calculate the minima of the free energy and then draw a common tangent line between them, but in this case there doesn't seem to be any minima. Also, it appears that the free energy of the solid phase is lower than that of the liquid phase even for low densities. Is this even possible? Or should I conclude that my plots are incorrect?
 
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  • #2
Are you sure those equations are meaningful in the full [0,1] range? Especially: How do you get a packing density η > 0.741? (I think it is not an accident that the spike of the solid line is there).

There are materials which do not have a liquid phase at a specific temperature, independent of the packing density.
 

What is a phase diagram?

A phase diagram is a graphical representation of the different phases of a substance, such as solid, liquid, and gas, and how they change in relation to temperature and pressure. It shows the conditions under which these phases exist and can help predict phase transitions.

What is coexistence in a phase diagram?

Coexistence in a phase diagram refers to the simultaneous existence of two or more phases of a substance under specific conditions of temperature and pressure. This can occur when the substance is in a state of equilibrium, where the rate of transformation between phases is equal.

What is the significance of coexistence in a phase diagram?

The presence of coexistence in a phase diagram is significant because it indicates a balance between two or more phases of a substance. This balance can be used to determine the conditions at which a substance can exist in different phases, and can also provide information about the properties and behavior of the substance.

How is coexistence determined in a phase diagram?

Coexistence in a phase diagram is typically determined by conducting experiments or calculations to determine the conditions at which two or more phases of a substance can exist in equilibrium. These conditions are often represented by lines or curves on the phase diagram, known as coexistence curves.

What factors can affect coexistence in a phase diagram?

The most influential factors that can affect coexistence in a phase diagram are temperature and pressure. Changes in these conditions can cause the substance to shift between phases, resulting in changes in the coexistence points and curves on the phase diagram. Other factors such as the composition and properties of the substance can also play a role in coexistence.

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