The Microscopic View

When a solid or a liquid evaporates to a gas in a closed container, the molecules cannot escape. Some of the gas molecules will eventually strike the condensed phase and condense back into it. When the rate of condensation of the gas becomes equal to the rate of evaporation of the liquid or solid, the amount of gas, liquid and/or solid no longer changes. The gas in the container is in equilibrium with the liquid or solid.

Factors That Affect Vapor Pressure

Surface Area: the surface area of the solid or liquid in contact with the gas has no effect on the vapor pressure.

Types of Molecules: the types of molecules that make up a solid or liquid determine its vapor pressure. If the intermolecular forces between molecules are: relatively strong, the vapor pressure will be relatively low. relatively weak, the vapor pressure will be relatively high.

Temperature: at a higher temperature, more molecules have enough energy to escape from the liquid or solid. At a lower temperature, fewer molecules have sufficient energy to escape from the liquid or solid.

Microscopic equilibrium between gas and liquid at low temperature. Note the small number of particles in the gas.

Microscopic equilibrium between gas and liquid at high temperature. Note the large number of particles in the gas.

Vapor Pressure
Suppose we have a closed container into which we pour some water. As soon as we add the water we check a pressure gauge connected to the container. We let the container sit for a while and then we check the pressure again. What might the pressure guage indicate? As the water evaporates the pressure exerted by the vapor above the liquid increases, until at some point, the pressure reaches a constant value, the vapor pressure of the substance:

The molecular basis of vapor pressure The kinetic energy of the molecules at the surface of a liquid varies over a range of values:

Some of the molecules have enough kinetic energy to overcome the attractive forces between the molecules The weaker the attractive forces, the greater the fraction of molecules with enough kinetic energy to escape The greater the fraction of molecules which can escape the liquid, the greater the vapor pressure Not only can water molecules leave the surface, but molecules in the vapor phase can also hit and go into the water Initially, there are no molecules in the vapor phase and the number of molecules in the vapor which are rejoining the water is zero As time goes on there are more molecules in the vapor phase and the number of a vapor molecule striking the water increases At some point in time the number of vapor molecules rejoining the water equals the number leaving to go into the vapor phase an equilibrium has been reached, and the pressure has stabilized at the characteristic vapor pressure of the substance

What if molecules in the interior of the liquid decides to leave the liquid phase and go into the vapor phase?

This interior bubble will rapidly collapse if the external pressure is greater than the vapor pressure If the external pressure is equal to, or lower than the vapor pressure, then the bubble will remain or expand and the liquid boils

Vapor Pressure
The boiling point of a liquid is the temperature at which its vapor pressure equals atmospheric pressure. The normal boiling point is the temperature at which its vapor pressure is 760 torr.