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In this chapter, we shall investigate the thermodynamics of phase equilibria. Our first concern will be with the nature of the phase diagrams of typical single component systems.

1.1 Liquid Vapor Equilibria.

If we place a sample of a liquid in an open dish, it will evaporate. The molecules of the sample will leave the surface of the liquid and become a part of the atmosphere. The vaporization process will usually continue until no more liquid remains. If, on the other hand, we place the sample of liquid in a closed vessel the vaporization process will generally be limited. Instead of the vapor molecules disappearing into the atmosphere, they have the opportunity to return to the liquid state. Thus we have a two - way traffic with molecules both leaving and returning to the liquid sample. It is instructive to consider how those two rates vary with time. We assume that time = 0 occurs at the moment that the lid is placed on the container.




Vapor Liquid



The rate of passage of molecules from the liquid state to the vapor state will depend upon the temperature and the surface area. We can ensure that the temperature remains constant and, by having a cylindrical vessel, also keep a constant surface area. At time = zero, there will be no molecules in the vapor phase to return to the liquid state. The number of molecules, in the vapor phase, will rise with time and thus the rate of their return will also rise. Eventually the rate of gas molecules will catch up with the liquid liquid

gas rate. At that time, we will have

created a dynamic phase - equilibrium. From that point on the two rates will stay the same but there will continue to be transfer of molecules between the two phases. We say that the vapor has become saturated. For any given temperature there is a specific saturation vapor concentration and consequently a saturation vapor pressure. It is this saturation vapor pressure that we usually refer to when we use the abbreviated term vapor pressure. This can create some confusion if one is not careful. It is very rare, for example, for our atmosphere to be saturated with water vapor, even if one lives in Louisiana and especially if one lives in New Mexico. Our next concern is with the temperature dependence of the vapor pressure. The rate at which molecules leave the liquid state and enter the gas phase is proportional to the fraction of molecules that reach the surface with sufficient kinetic energy to overcome the attraction of the other molecules. We can draw a graph of the kinetic energy distribution for the molecules reaching the surface.

8/27/2004 THERMODYNAMICS CHAPTER 5 Fraction of molecules with kinetic energy KE T1 T2


In this graph T2 > T1 . Emin is the minimum kinetic energy required for a molecule to escape the liquid phase. One sees that the fraction of molecules that have a kinetic energy greater than Emin is substantially higher at T2 than at T1. The conclusion is that the vapor pressure increases dramatically with increasing temperature. The next figure shows some typical vapor pressure curves. All have the same general shape. The highly volatile diethyl ether has substantially higher vapor pressures than does water.

1.2 Boiling.
The evaporation of a liquid can occur at any temperature. The phenomenon of boiling, however, takes place under very specific conditions.


Evaporation takes place at the surface of a liquid, boiling involves the formation of bubbles within the bulk. The bubble contains saturated vapor and is thus maintained by the vapor pressure of that liquid. Hindering the existence of the bubble is its external pressure. Squeezing the bubble is the prevailing atmospheric pressure plus a small hydrostatic contribution. Unless the vapor pressure matches or exceeds the external pressure on it, it will simply collapse or fail to form at all. Boiling commences at that temperature where the vapor matches the prevailing pressure. Our major concern is with the temperature at which a liquid boils when the pressure is atmospheric, or more precisely 760 torr. That is called the normal boiling temperature and is frequently represented by the symbol Tb . If the atmospheric pressure varies, so too will the boiling temperature. In El Paso Texas, the atmospheric pressure is typically 662 torr. That means a boiling temperature of about 96.3o C. Pressure cookers are designed to allow the pressure inside to build up to well over atmospheric pressure. That means that the water inside will boil at a higher temperature and that speeds up the rate of preparing steamed vegetables, for those who like that kind of thing. It is also possible to lower, by pumping, the pressure of the air in a distillation apparatus. That makes it possible to boil liquids, which might otherwise decompose or ignite, at a reduced temperature. The exact same curve that tells us how the vapor pressure varies with temperature can also be used to tell us how the boiling temperature varies with prevailing pressure. That curve is referred to as a liquid-vapor equilibrium curve. That is because at each combination, of prevailing pressure and temperature that lies on that curve, we have an equilibrium mixture of the liquid and the gas (vapor).

At any combination of p and T below and to the right of that curve we will find the substance existing as a gas. Above and to the left of the curve is a state where the substance is a liquid.



T This is, of course, only a part of the story. We will need to add into the same diagram an indication of the combinations of pressure and temperature where it is the solid that is the stable state.

1.3 Solid Vapor Equilibria.

Our first concern is with solid-gas equilibrium. We have to recognize that solids also have vapor pressures. At temperatures below the melting temperature, the vapor pressure of a solid is far lower than that of a liquid above the melting temperature. The general shape of the vapor pressure curve of a solid is very similar to that of a liquid. When the two vapor pressure curves are plotted on the same axes, they are seen to intersect.

Liquid Gas Triple Point. Solid Gas

T The combination of temperature and pressure at which the two curves intersect is called the triple point. The reason for the name is that, since one curve represents conditions for solid-gas equilibrium and the other those for


liquid gas equilibrium, the point of intersection must represent conditions in which all three phases are present in equilibrium


Solid Liquid Equilibrium

To complete the phase diagram of a substance we need to include the

melting point curve, which shows the combinations of temperature and pressure at which the solid and liquid are in equilibrium. The drawing above is of the phase diagram for water. It does not do a particularly good job of showing the way in which the vapor pressure curves for ice and liquid-water intersect. As the caption indicates, there is a significant exaggeration of the pressure dependence of the melting temperature of ice.

When pressure is applied to an equilibrium mixture of a solid and its liquid, there will be a tendency for the equilibrium to be shifted in the direction of that phase which is the more dense (compact). For the vast majority of substances, the solid is more compact than the liquid. One may argue that the more tidy


arrangement of the molecules or ions leads to better use of the space. That means that the normal situation finds the application of increased pressure favoring the solid state. That, in turn, results in an increase in the melting point with increasing pressure. Water is almost, but not quite, unique insofar as the liquid is denser than the solid (ice floats on water). That means that an increase of pressure favors the formation of liquid and that the melting point of water falls with increasing pressure. The substantial pressure exerted on ice by a skater on very thin blades causes the ice to melt and act as a lubricant. We note that the triple point occurs at a temperature of 0.01o C, which is obviously not much greater than the normal melting point value of 0.00oC. The triple point pressure of 4.6 torr is the lowest pressure at which water can exist as a liquid. Not shown on this phase diagram is the critical temperature above which water cannot exist in a liquid state. We shall have more to say about super critical fluids later. It is worth mentioning that the Kelvin and therefore Celsius (centigrade) unit of temperature is defines such that the triple point of water is exactly 273.16 K. The next figure represents the phase diagram for CO2. We notice first that the triple point pressure is of the order of 5 atm. That means that CO2 cannot possibly exist as a liquid at normal atmospheric pressure. At 1 atmosphere pressure, CO2 exists as a gas down to -77o C. At that temperature it condenses to form a solid, not a liquid. We note that, in this diagram, the authors have indicated the location of the critical point. Above the critical pressure, there is only one fluid phase. It is referred to as being supercritical.


The two phase diagrams that we have shown are relatively simple. Many substances, including water, change crystal structure when subjected to extreme conditions.


The Clapeyron Equation.

It is important to be able to predict the relationship between pressure and

temperature for phase equilibrium curves. We begin at any point on one such curve. The chemical potentials (molar Gibbs free energies) of the two phases are identical. If we change either the temperature or pressure, but not both, we will inevitably lose the equilibrium condition and one or other phase becomes stable. We can write the following equations for the free energy changes in phases A and B of a single pure component.


= - SA dT = - SB dT

+ VA dp + VB dp

To maintain equilibrium for a given pair of incremental changes dp and dT, we need for the two phases to have identical free energy changes. Thus:


- SA dT

+ VA dp

- SB dT

+ VB dp

S dT

V dp

dp / dT

= S / V

where S and V are the entropy and volumes changes associated with the phase change A

This is generally known as the Clapeyron equation. Since the free energy change G = 0, S = H / T. The equation may thus be rewritten in the form:

dp / dT
1.6 Solid Liquid Transitions.

= H / { T V }

Over modest temperature ranges the entropy and volume changes, arising from the conversion of solid into liquid, will remain virtually constant. That means that dp / dT will be roughly constant and the solid liquid equilibrium curve will appear to be linear. S for fusion will always be positive. For most substances, there is an increase in volume when a solid melts; i.e. V > 0. That means that dp / dT for the solid liquid curve will be positive. That implies that the melting temperature increases with increasing pressure. For water, the volume change is negative and thus dp / dT is negative. That is consistent with the melting temperature decreasing as the pressure increases.


Liquid Vapor Transitions.

There is a very useful approximation that describes the relationship

between pressure and temperature along a liquid vapor equilibrium curve. The first stage is the recognition that the molar volume of a gas is far larger than that of the liquid. That leads us to write the following approximation:

V = Vg - Vl = Vg



dp / dT dp / dT
which can be rearranged to give:

= H / { T Vg } = H p / RT2

Assuming the gas to be ideal, we can rewrite this in the form:

dp / p = H dT / RT2
Integration from T1 to T2 gives:

ln(p2/p1) = - Hvap/ R { T2-1 - T1-1}

This is the Clausius Clapeyron equation. If we know the enthalpy of vaporization at the normal boiling temperature, it permits us to determine the vapor pressure at any other temperature. If we combine this with Troutons rule (Hvap = 88 . Tb J mol-1), a knowledge of the boiling temperature is sufficient to predict the vapor pressure at some other temperature. The equation can also be used to determine enthalpies of vaporization from vapor pressure measurements at two or more temperatures.


Solid Vapor Equilibrium.

The approximations used to define the vapor pressure curves for liquids

can also be used for the vapor pressures of solids. In that case, the enthalpy of vaporization is replaced by that of sublimation.

ln(p2/p1) = Hsub/ R { T2-1 - T1-1}