TRANSITIONS BETWEEN PHASES

See the phase diagram for water, Figure 13.37. Lines connect all conditions of T and P where EQUILIBRIUM exists between the phases on either side of the line. (At equilibrium particles move from liquid to gas as fast as they move from gas to liquid, for example.)

Phase Diagram for Water

Animation of solid phase.

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Phase Diagram for Water

Animation of equilibrium between solid and liquid phases.

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Phase Diagram for Water

Animation of liquid phase.

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Phase Diagram for Water

Animation of equilibrium between liquid and gas phases.

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Phase Diagram for Water

Animation of gas phase.

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Phase Diagram for Water

Animation of equilibrium between solid and gas phases.

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Phase Diagram for Water

Animation of triple point. At the TRIPLE POINT all three phases are in equilibrium.
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Phases Diagrams
Important Points for Water
T(C) P(mmHg)

Normal boil point

Triple point

100
0.0098

760
760 4.58

Normal freeze point 0

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TRANSITIONS BETWEEN PHASES

As P and T increase, you finally reach the

CRITICAL T and P

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TRANSITIONS BETWEEN PHASES

As P and T increase, you finally reach the

CRITICAL T and P
Pcritical
.

Note that line goes straight up

High Pressure

LIQUID

Tcritical
GAS High Temperature

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TRANSITIONS BETWEEN PHASES

As P and T increase, you finally reach the

CRITICAL T and P
Pcritical
.

Note that line goes straight up

LIQUID

Tcritical
GAS High Temperature

Above critical T no liquid exists no matter how high the pressure.

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High Pressure

Critical T and P
COMPD H2O Tc(oC) 374 Pc(atm) 218

CO2
CH4 Freon-12 (CCl2F2)

31
-82 112

73
46 41

Notice that Tc and Pc depend on intermolecular forces.

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Solid-Liquid Equilibria
In any system, if you increase P the DENSITY will go up. Therefore as P goes up, equilibrium favors phase with the larger density (or SMALLER volume/gram).

Liquid H2O Density cm3/gram 1 g/cm3 1

Solid H2O 0.917 g/cm3 1.09

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Solid-Liquid Equilibria
In any system, if you increase P the DENSITY will go up. Therefore as P goes up, equilibrium favors phase with the larger density (or SMALLER volume/gram).

Liquid H2O Density cm3/gram

ICE
favored at low P
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Solid H2O 0.917 g/cm3 1.09

1 g/cm3 1
favored at high P

LIQUID H2O

Solid-Liquid Equilibria
ICE
favored at low P

LIQUID H2O
favored at high P

Solid H2O
760 mmHg

Liquid H2O

Normal freezing point

0 C
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Solid-Liquid Equilbria
Raising the pressure at constant T causes P water to melt. The NEGATIVE SLOPE of the S/L line is unique to H2O. Almost everything else has positive slope.
Solid H 2O 760 mmHg
0C

Liquid H 2O

Normal freezing point

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The behavior of water under pressure is an example of LE CHATELIERS PRINCIPLE At Solid/Liquid equilibrium, raising P squeezes the solid. It responds by going to phase with greater density, i.e., the liquid phase.
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Solid-Liquid Equilbria
P
Solid H2O 760 mmHg 0C Liquid H2O Normal freezing point

Solid-Vapor Equilibrium
At P < 4.58 mmHg and T < 0.0098 C

solid H2O can go directly to vapor. This process is called SUBLIMATION

This is how a frost-free refrigerator works.

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