Chapter 5 - Chemical Potential and Fugacity

Gibbs Energy and Temperature Gibbs Energy and Pressure Chemical Potential Real Gases - Fugacity

Variation of G with T

The variation of Gibbs energy with temperature is determined by the entropy.

(MG/MT)p = -S The most stable phase is the one with the lowest Gibbs energy.

Solid

This also has the lowest chemical potential, as we shall see.

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Variation of G with p

The variation of Gibbs energy with pressure is determined by the volume.

(MG/Mp)T = V In integral form, G(p) - G(po) = IVdp

p]

[limits: po to

For a perfect gas, use V = nRT/p to get For liquids and solids, use kT = -(1/V) (MV/Mp)T, and consider kT to be constant; get ln[V(p)/V(po)] =kTDp or V(p) = V(po)exp[- kTDp]. Two approx.: Dp . p for p>>po and exp[- kTp] .(1- kTp) Y V(p).V(po)[1-kTp]
o o o 2 o2
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G(p) = G(po) + nRT ln (p/po)

Chemical Potential

The chemical potential of a pure substance is defined as

m = (MG/Mn)T,p

For a pure substance, the Gibbs energy = G = n Gm, so

m = (MnGm/Mn)T,p = Gm For instance, the Gibbs energy of a perfect gas at pressure p was given as

G(p) = G(po) + nRT ln (p/po), which means that m = mo + RT ln (p/po) [Note m is an intensive quantity.]

Introducing Fugacity
m = mo + RT ln (p/po) is for perfect gases. What to do for imperfect (real) gases. Can define a different chemical potential function (call it m) such that

m = mo + RT ln (p/po)

Or can use the real gas pressure instead of the perfect gas pressure, using some equation of state other than pV = nRT Or can define a fugacity (effective pressure), f, and m = mo + RT ln (f/po)

Using Fugacities
Fugacities should be used instead of pressure for all functions of a real gas involving chemical potential. This includes equilibria and equilibrium constants.

Example: For the formation of ammonia, N2 + 3 H2 --> 2 NH3, elementary chemistry courses have used Kp = p2NH3 / pN2 pH23 Now we shall use K = f2NH3 / fN2 fH23

Interpreting Fugacities

Standard state of a real gase

The standard state of a real gas is the hypothetical state in which the gas is at a pressure po and behaving perfectly.

The relation between fugacity and pressure is

f=fp where f is the dimensionless fugacity coeffient.

m in terms of f and f
Since m = mo + RT ln (f/po), and f = f p, this means that m = mo + RT ln (p/po) + RT ln f The fugacity coefficient can be related to the compression factor, Z = pVm/RT ln f = I(Z - 1)/p dp [limits: 0 to p]

For any gas, as p 6 0, f 61. (I.e., any gas is perfect at zero pressure.)
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Fugacity of a van der Waals Gas

If the repulsive term is dominant in a van der Waals gas, then p = RT/(Vm - b)

Vm = RT/p + b

This leads to ln f = bp/RT

So Z = pVm/RT = 1 + pb/RT

If the attractive term is dominant in a van der Waals gas, then p = RT/Vm - a/Vm2, Y pVm2 - RTVm + a = 0
By the quadratic equation, Vm = RT [(RT)2 - 4ap)].5 . 2p If p is sufficiently low, (RT)2 >> 4 ap, so Vm = RT/p and Z = 1 - ap/(RT)2

This leads to ln f = -ap/(RT)2

Estimating Fugacities

The figures below can be used to estimate fugacities when the reduced temperature and pressure are known.

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