IB5201 Thermodynamics for Biotechnologists

Handout Material

Clapeyron and Clausius-Clapeyron Equations

The Clapeyron Equation

In a one-component phase diagram the lines separating the phases (for example, solid from liquid, liquid
from vapor, and so on) are not arbitrary, they are determined by the principles of thermodynamics and
equilibrium. Thermodynamics provides an equation for each line which gives pressure, p, as a function of
temperature T, in other words an equation of the form p = p(T) . It is now our task to find the form of the
function p(T). The diagram below is a portion of a hypothetical phase diagram and the phase line on this
diagram separates the phases α and β. In other words, the phases α and β are in equilibrium with each
other at any and all points on the line.

Phase transitions occur at constant temperature and pressure at the points on this line. Consider the phase
transition,

α → β. (1)

Since the α and β phases are in equilibrium with each other at any point on the line we know that the
change in the Gibbs free energy for the transition given by Equation 1 is zero everywhere on the α-β
phase line. That is,

ΔG = 0. (2)

We already know that for any process at constant temperature it must be true that

ΔG = Δ H − TΔS, (3)

so that

Ramachandran Palpandi Raja, Department of Biotechnology, Anna University Chennai

 IB5201 Thermodynamics for Biotechnologists
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(4)

for a phase transition.

The various quantities appearing in these equations are defined as usual by,

ΔG = Gβ − Gα, (5)

ΔS = Sβ − Sα. (6)

ΔH = Hβ − Hα. (7)

We will also define ΔV the same way,

ΔV = Vβ − Vα. (8)

As we have already said, ΔG = 0 along the α-β phase line. That is, ΔG is constant along the line and it is
being held constant at the particular value of zero. We want the slope of the line. Therefore, the derivative

we want is, . We can write this derivative in terms of quantities we know using the cyclic rule
(Euler's chain relation) as,

. (9)

We know from dG = − SdT + Vdp, or dΔG = − ΔSdT + ΔVdp , that

(10)

and

. (11)

Using Equations10 and 11 in Equation 9 (the two minus signs cancel) we get,

. (12)

Ramachandran Palpandi Raja, Department of Biotechnology, Anna University Chennai

 IB5201 Thermodynamics for Biotechnologists
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Equation 12 is the Clapeyron equation. The Clapeyron equation is thermodynamically exact. It contains
no approximations. There is another version of the Clapeyron equation which we obtain by inserting
Equation 4 for ΔS into Equation 12,

. (13)

Equation 13 is useful when we want to integrate dp to find p as a function of T. The integration of

Equation 12 or 13 is easiest if we can make the approximation that either ΔS or ΔH is reasonably constant
over the temperature range. However, ΔH usually varies more slowly with temperature than does ΔS, so
that the approximation is better when we integrate 13. Prepare Equation 13 for integration,

. (14)

To integrate Equation 14 we must know how ΔH and ΔV depend on temperature. We have already said
that ΔH can be regarded as approximately constant, but what about ΔV? ΔV is certainly not even near
constant if one of the components of the phase transition is a gas (see the next section), but if the
transition is solid → solid or solid → liquid we can approximate ΔV as a constant also. Then Equation 14
integrates to,

. (15)

If we let T2 and p2 range over the phase line and call them T and p, respectively, we can write pressure as
a function of temperature for a solid → solid or solid → liquid phase transition line as follows,

(16)

The Clausius-Clapeyron Equation

Equations 12 and 13 are exact and are valid for all types of phase transitions, solid → liquid, solid → gas,
liquid → gas, and so on. However, for solid → gas and liquid → gas phase transitions we can make two
approximations which will give us a very useful equation called the Calusius-Clapeyron equation. The
first approximation comes from noting that the volume of a given amount of gas is much larger that the
volume of an equivalent amount of solid or liquid. This being true, we can approximate ΔV by the volume
of the gas. That is,

ΔV = Vgas − Vliquid ≈ Vgas (17)

or

ΔV = Vgas − Vsolid ≈ Vgas . (18)

Ramachandran Palpandi Raja, Department of Biotechnology, Anna University Chennai

 IB5201 Thermodynamics for Biotechnologists
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In the second approximation we replace Vgas by the volume the gas would have if it were ideal. That is,
we set Vgas = nRT/p. With these two approximations Equation 13 becomes

, (19)

where the bar over the enthalpy, H, means that it is the enthalpy per mole. Equation 19 is the Clausius-
Clapeyron equation. We should emphasize that Equation 19 is not exact (because it contains two
approximations) and it only applies when one of the phases in the phase transition is a gas. Equation 19
can be prepared for integration is follows,

. (20)

Equation 20 can be integrated if we know how ΔH changes with temperature or, as we will now do, if we
regard ΔH as approximately constant. With the ΔH regarded as constant Equation 20 integrates to

(21)

Equation 21 is the integrated form of the Clausius-Clapeyron equation. If we want pressure as a function
of temperature we can let the point (p2, T2) range over the phase line and call it simply (p, T) and then take
the antilog of both sides,

. (22)

Notice that if we know two points on the curve we can solve for ΔH, or if we know one point on the curve
and ΔH we can solve for any other point or even get the entire curve. Equation 22 is very useful for
estimating vapor pressures at various temperatures when ΔH and the vapor pressure at one temperature
are known.

Other details and interesting stuff

1. You can get fancy with Equations 19 and 20 if you want. For example, we know that ΔH for a phase
transition is not really constant. If we wanted to take into account the temperature dependence of ΔH we
need to know the heat capacities of the two phases, or rather the difference in the heat capacity for the two
phases,

ΔCp = Cpβ − Cpα. (23)

Then

Ramachandran Palpandi Raja, Department of Biotechnology, Anna University Chennai

 IB5201 Thermodynamics for Biotechnologists
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. (24)

Initially we regarded ΔH as constant. The next level of approximation would be to regard ΔCp as constant
so that,

. (25)

Using this expression for ΔH in Equation 20 we get

, (26)

or,

. (27)

Equation 27 integrates to,

(28)

You can get even fancier. The next level of approximation would be to include the temperature
dependence of the heat capacities, but we won't deal with that here.

2. Equation 12 does not depend on ΔG being zero. It only assumes that ΔG is constant for the α → β
transition. Of course, if ΔG is not zero then equation 4 is not true which makes Equation 13 invalid.
Further, if ΔG is not zero then either the α phase or the β phase is thermodynamically unstable. (We
usually use the word metastable to describe this situation. Examples are supercooled liquids, superheated
liquids, supercooled vapors, and some metastable solids - like diamond.) Nevertheless, one can visualize a
family of curves running along side the phase diagram curve with ΔG constant at some value other than
zero.

The Melting Curve for Water; Vapor Pressure

The melting curve for water

We mentioned in our initial discussion of one-component phase diagrams that the slope of the melting
curve for water was negative.

Ramachandran Palpandi Raja, Department of Biotechnology, Anna University Chennai

 IB5201 Thermodynamics for Biotechnologists
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Water is one of just a few known substances with this feature (bismuth is another), the melting curve for
most substances has a positive slope. Let us consider the thermodynamics consequences of this negative
slope. Since we are talking about the melting curve we must use the Clapeyron equation,

(1)

where, of course, the ΔS and ΔV refer to the melting process or the freezing process. For the purposes of
this discussion let us consider the melting process. That is, we will assume that the phase change is

H2O(s) → H2O(l).

A negative slope on the phase diagram means that the derivative in Equation 1 is negative. This in turn
requires that,

(2)

We know that ΔS for the melting process is positive because the system is going from the highly ordered
crystalline solid state to the more disordered liquid state (and we can calculate it from ΔS = ΔHfusion/Tmp).
Therefore, the only way the derivative in Equation 2 can be negative is if ΔV is negative. This means that
the molar volume of the liquid is smaller than the molar volume of the solid at the melting point,

Ramachandran Palpandi Raja, Department of Biotechnology, Anna University Chennai

 IB5201 Thermodynamics for Biotechnologists
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(3a, b)

Taking the reciprocal of Equation 3b we find that,

(4)

and, since the density is proportional to the reciprocal of the volume, this means that the density of the
liquid is greater than the density of the solid (at the melting point).

This result is counterintuitive. We expect that materials will expand on melting and most materials do
expand on melting. However, water is unusual in this respect and contracts on melting. The visible
consequence of this fact is that ice floats on liquid water. We are so accustomed to this that we do not
even notice that it is unusual. However, if you have worked in the laboratory with other solid/liquid
systems you will be aware that most often the solid sinks in the melt.

You can argue that the slope of the melting curve of water makes a crucial contribution to the ability of
our planet, Earth, to support life. If the slope were positive then ice would sink in water. In cold climates
ice would form in winter and sink to the bottom. This ice would be insulated from the summer warmth by
the layer of water above it and would only partially melt. The next winter more ice would accumulate on
the bottom. Eventually, all rivers and lakes and possibly a large portion of the oceans would be frozen
from the bottom up with only a shallow layer of liquid water being formed on the surface during the
summer. There would likely be no animal or plant life in these frozen lakes and rivers.

Vapor pressure - What is vapor pressure?

We mentioned in our discussion of one-component phase diagrams that the vaporization curve is
sometimes referred to as the vapor pressure curve. This is because this curve - along with the sublimation
curve - gives a plot of the vapor pressure of the substance versus temperature.

The vapor pressure is a measure of the ability of molecules to escape from the surface of a solid or liquid.
The following discussion uses ideas that are outside the scope of thermodynamics, but they may be useful
in calibrating our intuition. A solid or liquid is held together by intermolecular attractive forces. However,
the molecules have kinetic energy (energy of motion) which we will later see is proportional, on the
average, to the Kelvin temperature. There is a competition. The attractive forces are trying to keep the
molecules in the solid or liquid and the kinetic energy is trying to take them out. The vapor pressure is the
net result of this competition.

As more and more molecules build up in the space above the solid or liquid more of them will collide
back with the surface and some of them will stick. At a fixed temperature the system will reach a state of
"dynamic equilibrium," where just as many molecules escape from the surface as collide back and stick.
At this point the pressure exerted by the molecules in the space above the solid or liquid is, by definition,
the vapor pressure of the solid or liquid.

Ramachandran Palpandi Raja, Department of Biotechnology, Anna University Chennai

 IB5201 Thermodynamics for Biotechnologists
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As the temperature is increased the average kinetic energy increases so more molecules are able to
overcome the intermolecular forces and the vapor pressure increases.

Increasing the vapor pressure by the application of an external pressure

One can also increase the vapor pressure of a solid or liquid by applying an external pressure. This effect
is not as easy to understand qualitatively as the effect of temperature, but it is easy to calculate
thermodynamically. Recall that for solids and liquids, which are not very compressible over relatively
small pressure ranges, the Gibbs free energy change is given by,

(5)

In words, Equation 5 says that G increases when we "squeeze" a solid or a liquid. (The Gibbs free energy
of a gas also increases when you "squeeze it, but gases are quite compressible so that Equation 5 does not
hold for gases.) We would expect that if the Gibbs free energy of a solid or liquid increases its vapor
pressure would also increase. We shall see if this is true. Rewrite Equation 5 as follows,

(6)

We will rearrange Equation 6 and then divide it by the number of moles of substance, n.

(7a, b, c, d)

In Equation 7d we have used the fact that the Gibbs free energy per mole is called the chemical potential
and is symbolized by a lower case Greek "mu."

Let us consider two systems, all at temperature, T. The first system is a closed container which contains
only, say, liquid water and water vapor in equilibrium. Since the system is in equilibrium the chemical
potential of the liquid water and water vapor must be equal. Using the approximation that the vapor is an
ideal gas we can write,

(8a, b)

Ramachandran Palpandi Raja, Department of Biotechnology, Anna University Chennai

 IB5201 Thermodynamics for Biotechnologists
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(In Equation 8b we have used the expression for the variation of the chemical potential of an ideal gas
with pressure.)

Our second system consists of a similar container of liquid water and water vapor, but also contains an
inert gas, say air, at a pressure, P. It is the air that is squeezing the liquid and providing the "external
pressure." We will call this system the "prime" system. In this second system the chemical potentials of
the liquid water and water vapor must still be equal, but they are not equal to the same values as in the
first system. In the "prime" system we have,

(9)

but

(10)

and

(11)

So we have two equations equating chemical potentials in the gas and liquid phases, one for the first
system and one for the second system.

(12)

and

(8b)

When we subtract Equation 8b from Equation 12 we eliminate all the standard state chemical potentials
and are left with

(13a, b)

so that

(14)

Ramachandran Palpandi Raja, Department of Biotechnology, Anna University Chennai

 IB5201 Thermodynamics for Biotechnologists
Handout Material

Equation 14 tells us that the vapor pressure of the liquid, in this case water, increases when we apply an
external pressure. For water the vapor pressure increases by 0.074 % at 1.00 atm and 7.6 % at 100 atm.

Ramachandran Palpandi Raja, Department of Biotechnology, Anna University Chennai