Phase Diagrams – Examples

Chem 153: Physical Chemistry I (Santiago)

I knew it. We never coexist. You played my heart. We are always on the triple point.

 Phase Diagram and Variance. The variance varies all over the phase diagram, as shown
below.

 Carbon Dioxide Phase Diagram. The phase diagram of CO2 is shown below. The
increasing slope of the solid-liquid coexistence curve is normal to most substances. The
triple point of CO2 lies at 5.11 atm and 216.8 K. This explains why CO2 sublimes at normal
atmospheric pressure, because CO2 can only be liquefied above 5.11 atm. This reflects the
weakness of the intermolecular forces between the nonpolar carbon dioxide molecules.

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 Water. The phase diagram of water is shown below. One very noticeable feature is the
negative slope of the solid-liquid coexistence curve. This can be seen because ice is less
denser than water because of its open cage structure. Also, the phase diagram shows several
solid phases other than the ordinary ice (Ice I). Each one occurs at specific T and p.

 Helium. The phase diagram of Helium-4 is shown below. Pure Helium-4 has two liquid
phases. He-I behaves like a normal liquid, He-II behaves as a superfluid. Superfluid flows
without viscosity. Helium is the only known substance with a liquid-liquid boundary, called
the λ-line.