Thermodynamics Lecture 13 Vapor pressures from another viewpoint

1. Properties of ideal gas mixtures (Ch 8)

We have used PV = nRT, where n is the number of moles of gas molecules in a
system of fixed volume. If, instead of having a pure gas, we have a mixture of
different types of gas molecules, then ntot = nA + nB + nC +…. . That is, the total
moles in the system is the sum of the moles of the individual species. We can also
define the total pressure in the system as the sum of the partial pressures due to each
specie. Then Ptot = PA + PB + PC +…. The mole fractions of species and partial
pressures of species are related because:

PA/ Ptot = (nA x RT/V)/ (ntotx RT/V) = nA / ntot = XA , the mole fraction A in the
system.

PA = XA Ptot We can express the composition of the gas mixture either as a mole
fraction or as a partial pressure. Note that if Ptot = 1 atm, the numerical value of XA
and PA are the same.

Also note that if we blend pure gases at a constant total pressure, nA = VAPtot /RT, and
ntot = VtotPtot /RT, so nA / ntot = VA / Vtot . Therefore, we can use volume fractions as
equivalent to mole fractions in these mixtures.

2. Gibbs Free energy change for isothermal expansion of an ideal gas.

If T is constant, then dG = VdP = RT/PdP. For expansion from P1 to P2, G =
Int(RT/PdP) (P1, P2) = RT ln(P2/ P1)

This applies whether the gas is expanding into vacuum, or whether it is mixing with
another gas, such that P2 would be a partial pressure.
If one mole of pure gas A at pressure Ptot mixes with another gas so that its pressure
drops to partial pressure PA, the Gibbs Free Energy change is
Gmix = RTln PA/ Ptot = RT ln XA . We’ll call this the partial molar Gibb Free
Energy of mixing of A in the system, since this is the Gibbs free energy change to
mix one mole of A into the system.

If we have nA moles of A atoms and nB moles of B atoms, such that nA + nB = ntot =

one mole, the Gibbs Free energy of mixing to form one mole of the solution is
Gmix = nA GmixA + nB GmixB = nA RTln PA/ Ptot + nB RTln PB/ Ptot = XA RT ln XA
+ XB RT ln XB .

This is called the integral molar Gibbs Free energy of mixing of the solution.

Recall that the integral molar entropy of mixing was: Smix = -(XA R ln XA
+ XB R ln XB ).

Then Gmix = Hmix - TSmix . Then for Gmix = XA RT ln XA + XB RT ln XB .

= - TSmix . That is Hmix = 0.
We can see that this should be true for an ideal gas mixture. Hmix results from the
changes in the chemical bond strengths between the pure materials and the solution,
but for ideal gases, there are no chemical bonds between the gas molecules, so there
can’t be a change in their strength. Hmix = 0, is a general characteristic of ideal
solutions, of which ideal gases are one example. We will find that there are other
examples as well, but we can do quite a few things by considering the gas phase to be
an ideal solution and all of the condensed phases as pure materials in their standard
states.

For example, another way to look at sublimation vapor pressures is as a chemical

reaction:

A(s) = A(g)

The reaction is at equilibrium when the Gibbs Free Energies of A in the solid and the
gas phases are the same, therefore,
Greaction = Ggas – Gsolid = 0 at equilibrium
. In general, we need to use the partial molar Gibbs Free Energy to make this
calculation, but we know that the solid is the pure solid in its standard state, then
Gsolid = Gsolid0 .
The gas may not be in its standard state, if we are not at the boiling point and P is not
1 atm. Then
Ggas = Ggas0 + RTlnPA = Ggas0 + RTlnXA + RTlnPtot, if the A is evaporating into a
mixture of gases at some fixed total pressure.

Then Greaction = Ggas0 + RTlnPA - Gsolid0 . = Gsublimationo + RTlnPA .

At equilibrium, Greaction = 0, so RTlnPA = -Gsublimationo . or

lnPA = -Gsublimationo /RT if cp = 0, then
lnPA = -Hsublimationo /RT + Ssublimationo /R, = -Hsublimationo /RT + Integration constant,
the same as we found from the Clapeyron equation. If we included the cp term, it
would be the same as well. An advantage of looking at it this way is to remember
that
lnPA = lnXA + lnPtot, so if substance A is evaporating into an inert gas, we can use this
equation to calculate the composition of the gas in equilibrium with solid A.
PA = exp (-Gsublimationo /RT) = XA Ptot,