Free Energy, Vapor Pressure and

the Equilibrium Between a Vapor

and Condensed Phase

References:

Thermodynamics, G. N. Lewis and M. Randall,

rev. K. Pitzer and L. Brewer, McGraw Hill, New
York (1961).

Chemical Thermodynamics, I. Klotz, Benjamin,

New York (1964).
 The Gibbs Free Energy is generally
agreed to be the weapon of choice for
describing (a) chemical reactions and (b)
equilibria between phases. It is defined
as:
G = H TS = E + PV TS (1)
Where H = Enthalpy
E = Total internal energy
T = [Absolute] Temperature
S = Entropy

Obviously dG = dE + PdV +VdP TdS SdT

 Aside
Remember that thermodynamic variables
come in pairs
One is intrinsic (does not depend on
system size)
One is extrinsic (depends on system size)
Examples: P and V, T and S
Also G and N, the number of moles of stuff
in the system.
Hence G is the appropriate variable when
material is moving between phases
 From the
First Law of Thermodynamics
dE = TdS PdV since dS = Q/T and
the mechanical work done on a system
when it expands is PdV.
Substituting into
dG = dE + PdV +VdP TdS SdT

Leaves: dG = -SdT + VdP

Apply equation to a closed system
Closed system contains pure substance
vapor
condensed phase
Phases co-exist in equilibrium.
Objective will be to see how the pressure
of the vapor depends on the temperature
of the system.
Write the Free Energy Equation twice
Once for each phase

dGc = -ScdT + VcdP c refers to the

condensed phase
dGv = -SvdT + VvdP v refers to the
vapor phase
 Objective of the Exercise
Change system temperature
See how the pressure of the vapor
changes
Note:
Both the vapor and condensed phase are in
thermal equilibrium
Both are at the same temperature
System remains in thermal equilibrium if the
molar free energy of the system, also known
as the chemical potential, remains constant.
 Definition of chemical equilibrium
between two phases
Free energy is the same in both phases
Gc = G v
Changes in free energy when some
independent variable is changed must be
the same if they are to remain in
equilibrium
 dGc = dGv
-ScdT + VcdP = -SvdT + VvdP
(Sv - Sc )dT = (Vv- Vc)dP
(Sv - Sc ) is the entropy change that takes
place when material moves from the
condensed phase to the vapor
S = Q/T where Q is the amount of heat
required per mole of material moved
between the phases
Q is just the heat of vaporization!
 dP/dT = (Sv Sc)/(Vv Vc) = Hv/(TV)

This is the Clapeyron equation (E.

Clapeyron, J. cole polytech. (Paris)
14(23), 153 (1834). It relates the change
in pressure of a vapor to the temperature
in a closed, mono-component system to
the heat of vaporization, system
temperature and molar volume change of
the material on vaporization.
 Creating of an Ideal Gas
For lack of a better model, we treat most
vapors as ideal gases, whose molar
volume is given by:
V/n = RT/P
Alternatively, equation of state is needed
Molar volume of gas is typically factor of
500 larger than condensed phase
Hence Vc is negligible in comparison
 Substituting and Integrating
dP = (Hv/Vv)dT/T = (PHv/RT)dT/T

dP/P = Hv/R)dT/T2

ln(P(T)/ P0) = -(Hv/R)(1/T 1/T0)

P(T) = P0 exp(-Hv/R(1/T 1/T0))

 The vapor pressure in equilibrium with a
condensed phase increases exponentially
(sort of: exp(-1/T) isnt exactly an
exponential!) with temperature from zero
up to the critical temperature.
Borne out in the vapor pressure charts
and generating functions for them.
Deviations from linearity on the log-log plot
Temperature dependence of the heat of
vaporization
exp (-1/T) isnt really linear in the exponent.
 Heat of Vaporization from CRC Data
Log10p(Torr) = -0.2185*A/T + B
Vapor Pressure of Water

10000

"Normal boiling point"

Vapor Pressure (Torr)

1000

100

10

0.1
-20 0 20 40 60 80 100 120

Temperature (C)
Generating Function s Imperfect
Normal boiling point of water on the plot is
about 108.2 C.
I cheated; I looked at the data!
What does Normal boiling point mean??
What does boiling mean???
 Kubaschewski, Evans and Alcock, Metallurgical
Thermochemistry, Pergammon, Oxford (1967)

Log10p(Torr) = A/T + BlogT + CT + D

Vapor Pressure of Water

10000
V apor P ressure (T orr)

1000 "Normal boiling point"

100

10

Kubaschewski et al.

0.1
-20 0 20 40 60 80 100 120

Temperature (C)
 From Kubaschewskis Data
Vapor pressure at 100 C is 758 Torr
Much better approximation!
Caveat emptor!
Life is like a sewer: the quality of the fit
depends on the number of terms in the
generating function!
 RCA Charts
Great resource tool: the RCA Charts,
which live in 327 JFB. Treat them with
great respect: they are much older than
you are and irreplaceable.
Often imitated
Never duplicated
 Other Sources of Data
Vapor Pressures of Pure Substances,
Daniel R. Stull, Industrial and Engineering
Chemistry, April 1947, pp. 517 550.
(Tables give data on temperature required
to generate a specific vapor pressure.)
Vapour Pressure of the Elements, An. N.
Nesmeyanov, Academic Press, NY, NY
(1963).
 Gibbs Phase Rule
F=CP+2
F = number of degrees of freedom
C = number of components
P = number of phases
What is a phase?
What is a component?
What is a degree of freedom?
Phase Diagram of Water

Melting
curve
Boiling curve

Normal boiling point

Melting
point

Sublimation curve
 Homework
1. Determine the vapor pressure at 77 K
Water
Carbon monoxide
2. What is the boiling point of water in a
vacuum system at 10-6 Torr?
3. What is the vapor pressure of carbon
dioxide at room temperature?
4. What is the condensed phase of carbon
dioxide in equilibrium with the vapor at
room temperature? How do you know?