Chem 2 Lec

Intermolecular Forces of Liquids and Solids; Phase Diagrams
Vocabulary:
Fluid
• A gas or a liquid; a substance that can flow.
Solid
• A phase of matter with definite shape and volume.
Liquid
• A phase of matter with definite volume but no definite shape.
Gas
• A phase of matter with no definite shape or volume of its own.
Vapor
• A gaseous substance that exists naturally as a liquid or solid at normal temperature.
Melting
• A phase change from solid to liquid.
Vaporization
• A phase change from liquid to gas.
Sublimation
• A phase change from solid to gas.
Condensation
• A phase change from gas to liquid.
Freezing
• A phase change from liquid to solid.
Deposition
• A phase change from gas to solid.
Melting (or freezing) curve
• The curve on a phase diagram which represents the transition between the liquid and solid states.
Vaporization (or condensation) curve
• The curve on a phase diagram which represents the transition between the gaseous and liquid states.
Sublimation (or deposition) curve
• The curve on a phase diagram which represents the transition between the gaseous and solid states.
Triple point
• The point on a phase diagram at which the three states of matter coexist.
Critical point
• The point in temperature and pressure on a phase diagram where the liquid and gaseous phases of a substance merge
together into a single phase. The temperature and pressure corresponding to this are known as the critical temperature and
critical pressure.
Normal melting and boiling points
• Melting and boiling points when the pressure is 1 atm.
What is a phase diagram?

A phase diagram is a graphical representation of the physical states of a substance under different conditions
of temperature and pressure. It gives the possible combinations of pressure and temperature at which certain physical
state or states a substance would be observed. Each substance has its own phase diagram. A typical phase diagram is
shown below.
What are the features of a phase diagram?
Phase diagrams are plots of pressure (usually in atmospheres) versus temperature (usually in degrees Celsius or
Kelvin). The diagram is divided into three areas: solid, liquid and gaseous states. The boundary between the liquid and
gaseous regions stops at point C, the critical temperature for the substance.
• Units of pressure:
• 1 atm = 101325 Pa (pascal)
• 1 atm = 760 torr (mmHg)
• Units of temperature: (K = ˚C + 273)
• 0 ˚C = 273 K, 100 ˚C = 373 K
A. The Three Areas
The three areas are marked solid, liquid, and vapor. Under a set of conditions in the diagram, a substance can exist in a solid,
liquid, or vapor (gas) phase. The labels on the graph represent the stable states of a system in equilibrium.
Suppose a pure substance is found at three different sets of conditions of temperature and pressure corresponding to A, B, and C
as shown in the following diagram:
Under the set of conditions at A in the diagram, the substance would be a solid as it falls into that area of the phase diagram. At B, it
would be a liquid; and at C, it would be a vapor (gas).
B. Three Lines (Curves)

The lines that serve as boundaries between physical states represent the combinations of pressures and temperatures at which two
phases can exist in equilibrium. In other words, these lines define phase change points.
1. The green line divides the solid and liquid phases, and represents melting (solid to liquid) and freezing (liquid to solid) points.
Melting (or freezing) curve – the curve on a phase diagram which represents the transition between liquid and solid states.
It shows the effect of pressure on the melting point of the solid. Anywhere on this line, there is equilibrium between the solid
and the liquid.
2. The blue line divides the liquid and gas phases, and represents vaporization (liquid to gas) and condensation (gas to liquid) points.
Vaporization (or condensation) curve – the curve on a phase diagram which represents the transition
between gaseous and liquid states. It shows the effect of pressure on the boiling point of the liquid. Anywhere
along this line, there will be equilibrium between the liquid and the vapor.
3. The red line divides the solid and gas phases, and represents sublimation (solid to gas) and deposition (gas to solid) points.
Sublimation (or deposition) curve – the curve on a phase diagram which represents the transition between
gaseous and solid states. It represents the effect of increased temperature on a solid at a very low constant
pressure, lower than the triple point.
C. Two Important Points

There are two important points on the diagram, the triple point and the critical point.
The triple point
The triple point is the combination of pressure and temperature at which all three phases of matter are at equilibrium. It is the point
on a phase diagram at which the three states of matter coexist. The lines that represent the conditions of solid-liquid, liquid-vapor,
and solid-vapor equilibrium meet at the triple point
• It is a unique combination of temperature and pressure where all three phases are in equilibrium together.
The critical point
The critical point terminates the liquid/gas phase line. It is the set of temperature and pressure on a phase diagram where the liquid
and gaseous phases of a substance merge together into a single phase. Beyond the temperature of the critical point, the merged
single phase is known as a supercritical fluid.
The temperature and pressure corresponding to this are known as the critical temperature and critical pressure.
If the pressure on a gas (vapor) is increased at a temperature lower than the critical temperature, the liquid vapor equilibrium line will
eventually be crossed and the vapor will condense to give a liquid.
These can be found from the phase diagram by drawing a line across pressure at 1 atm.
How does the phase diagram of water look like?
The Phase Diagram for Water
There is only one difference between the phase diagram for water and the other phase diagrams discussed. The solid-liquid
equilibrium line (the melting point curve) slopes backwards rather than forwards.
For water, the melting point gets lower at higher pressures. This is because solid ice is less dense than liquid water. This phenomenon
is caused by the crystal structure of the solid phase. In the solid forms of water and some other substances, the molecules crystallize
in a lattice with greater average space between molecules, thus resulting in a solid occupying a larger volume and consequently with
a lower density than the liquid. When it melts, the liquid water formed occupies a smaller volume
An increase in pressure will move the above equilibrium to the side with the
smaller volume. Liquid water is produced. To make the liquid water freeze again
at this higher pressure, the temperature should be reduced. Higher pressures
mean lower melting (freezing) points.
Identifying data from the phase diagram of water
Notice that the triple point for water occurs at a very low pressure, 0.006 atm and at 273.2 K temperature. Also notice that the critical
temperature is 647 K (374°C). It would be impossible to convert water from a gas to a liquid by compressing it above this temperature.
The critical pressure is 218 atm.
The normal melting and boiling points of water are found in exactly the same way as we have already discussed - by determining
where the 1 atm pressure line crosses the solid-liquid, and then the liquid-vapor equilibrium lines. The normal melting point of water
is 273 K (0 ˚C), and its normal boiling point is 373 K (100 ˚C).
How does the phase diagram for carbon dioxide look like?
The Phase Diagram for Carbon Dioxide
The only thing special about this phase diagram is the position of the triple point, which is well above atmospheric pressure. It is
impossible to get any liquid carbon dioxide at pressures less than 5.2 atmospheres.
At 1 atm pressure, carbon dioxide will sublime at a temperature of 197.5 K (-75.5 °C). This is the reason why solid carbon dioxide is
often known as "dry ice." There is no liquid carbon dioxide under normal conditions - only the solid or the vapor.
Activity 2
A. Refer to the following phase diagram of a certain substance to answer the following questions. Upload your answers in
EDMODO.
1. In what phase is the substance at 50 °C and 1 atm pressure?

2. At what pressure and temperature conditions will all three phases of the substance be present?
3. What is the normal melting point of the substance?
4. What phase(s) will exist at 1 atm and 70 °C?
B. Constructing a Phase Diagram

Visualize a substance with the following points on the phase diagram: a triple point at 0.05 atm and 150 K; a normal melting point
at 175 K; a normal boiling point at 350 K; and a critical point at 2.0 atm and 450 K. The solid liquid line is “normal” (meaning
positive sloping). For this, complete the following:
1. Roughly sketch the phase diagram, using units of atmosphere and Kelvin. Label the area 1, 2, and 3, and
points T and C on the diagram.
2. Describe what one would see at pressures and temperatures above 2.0 atm and 450 K.
3. Describe the phase changes from 50 K to 250 K at 1.5 atm.
4. What exists in a system that is at 1 atm and 350 K?
5. What exists in a system that is at 1 atm and 175 K?

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Chem 2 Lec

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Intermolecular Forces of Liquids and Solids; Phase Diagrams

What is a phase diagram?

B. Three Lines (Curves)

C. Two Important Points

1. In what phase is the substance at 50 °C and 1 atm pressure?

B. Constructing a Phase Diagram

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