12.

2 QUANTITATIVE ASPECTS OF PHASE CHANGES

In this section, we examine the heat absorbed or relased in a phase change and the equilibrium
nature of the process.
HEAT INVOLVED IN PHASE CHANGES : A KINETIC-MOLECULAR APPROACH
We can apply the kinetic-molecular theory quantitatively to phase changes by means of a heating-
cooling curve, which shows the changes that occur when heat is added or removed at a constant rate from
a particular sample of matter. To an observer, the process is continuous, but we can divide it into five
heat-releasing (exothermic) stages that correspond to the five portions of the curve- the gas cools, it
condenses to a liquid, the liquid cools, it freezes to a solid, and the solid cools a bit further :
Stage 1, Gaseous water cools.
Stage 2, Gaseous water condense, this Step contributes the greatest portion of the total heat released
because of the decrease in potential energy that occurs with the enormous decrease in distance between
molecules in a gas and those in a liquid.
Stage 3, Liquid water cools, the molecules have now condensed to the liquid state. The continued loss of
heat appears as a decrease in the most probable molecular speed.
Stage 4, Liquid water freezes, at the freezing temperature of water. 0 C, intermolecular attractions
overcome the motion of the molecules around one another.
Stage 5, Solid water cools, with motion restricted to jiggling in place, further cooling merely reduces the
average speed of this jigging

Two Key Points stand out in this or any similar process (at constant pressure), whether exothermic and
endothermic :
1. Within a phase, a change in heat is accompanied by a change in temperature, which is associated with a
change in average Ek as the most probable speed of the molecules changes.
2. During a phase change, a change in heat occurs at a constant temperature, which is associated with a
change in Ep, as the average distance between molecules changes.

THE EQUILIBRIUM NATURE OF PHASE CHANGES

In a closed container under controlled conditions, how ever, please changes of many substances
are reversible and reach equilibrium, just as chemical changes do.

Liquid-gas Equilibrium
A. In a closed flask at constant temperature with the air removed, the initial pressure is zero. As
molecules leave the surface and enter the space above the liquid, the pressure of the vapor rises
B. At equilibrium, the same number of molecules leave as enter the liquid within a given time, so the
pressure of the vapor reaches a constans value.
C. A plot of pressure vs, time shows that pressure of the vapor increases as long the rate of vaporization is
greater than the rate of condensation. At equilibrium, the rates are equal, so the pressure is constant. The
pressure at this point is the vapor pressure of the liquid at the temperature.

The Effects of Temperature and Intramolecular Forces on Vapor Pressure

The vapor pressure of a substance depends on the temperature. Raising the temperature of a liquid
increases the fraction of molecules moving fast enough to escape the liquid and decreases the fraction
moving slowly enough to be recaptured. In general, the higher the temperature is, the higger the vapor
pressure.
The vapor pressure also depends on the intermolecular forces present. The average Ek is the same
for different substances at a given temperature. Therefore, molecules with weaker intermolecular forces
vaporize more easily. In general, the weaker the intermolecular forces are, the higher the vapor pressure.

Solid-Liquid Equilibrium
Because liquids and solids is nearly incompressible, a change in pressure has little effect on the
rate of movement to or from the solid. Therefore, in contrast to the boiling point, the melting point is
affected by pressure only very slightly and plot of pressure (y axis) vs temperature (x axis) for a solid-
liquid phase change is typically a straight, nearly vertical line.

Solid-Gas Equilibrium
Solids have much lower vapor pressures than liquids. Sublimation, the process of a solid
changing directly into a gas, is much less familiar than vaporation because the necessary conditions of
pressure and temperature are uncommon for most substances.

PHASE DIAGRAM : EFFECT ON PRESUURE AND TEMPERATURE ON PHYSICAL STATE

A phase diagram has these 4 features :
1. Regions of The diagram. Each region corresponds to one phase of the substance.
2. Lines Between regions. The lines separating the regions represent the phase-transition curves discussed
earlier.
3. The Critical Point.
4. The Triple Point. The 3 phase-transition curves meet at the triple point : the pressure and temperature at
which 3 phases are in equilibrium.