APPENDIX 1

Basic Fluid Thermodynamics

A system may undergo a spontaneous change for one or both of two

reasons.
1. To minimize energy.
2. To maximize entropy.
Gibbs free energy is a measure of both of these, and for any change
occurring at a constant external pressure p the change in free energy (DG)
tells us whether the change will occur spontaneously or not (Fig. A1.1).
Now:
DG ¼ DE þ pDV  T DS [A1.1]

where DG ¼ change in Gibbs free energy; DE ¼ change in internal energy;

DV ¼ change in volume; and DS ¼ change in entropy.

GIBBS FREE ENERGY OF MIXING

If DG is negative (due to negative DE or positive DS, or both) the change
will occur spontaneously.
Consider the mixing of a number of components.
Looking at a simple two-component system:
DG mixing ¼ DE mixing þ pDV  T DSmixing [A1.2]

ΔGA>B

B
Figure A1.1 Gibbs free energy of mixing.

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198 Appendix 1: Basic Fluid Thermodynamics

ENTROPY OF MIXING
DSmixing is always positive.
Entropy depends on the number of possible “arrangements” of mole-
cules, and in mixtures it is always more than in separate phases, therefore
mixing will always occur from the entropy effect due to the negative third
term in the equation for DGmixing. The entropy change of mixing is shown
in Fig. A1.2b for a two-component mixture.

INTERNAL ENERGY OF MIXING

For a two-component mixture, if the attractive interaction between types 1
and 2 molecules is less than the average between types 1 and 1 and 2 and 2,
then DEmixing will be positive for all mixtures (Fig. A1.2b).

GIBBS FREE ENERGY OF MIXINGdCOMBINATION

OF TERMS
DGmixing ¼ DEmixing þ pDV  T DSmixing [A1.3]
Combining entropy and internal energy effects will thus reduce free
energy by splitting into coexisting phases a and b, as shown in Fig. A1.2c.

Figure A1.2 Gibbs free energy of a two-component mixture. (a) Entropy of mixing;
(b) Internal energy of mixing; (c) Total Gibbs free energy of a two-component mixture.
 Appendix 1: Basic Fluid Thermodynamics 199

Figure A1.3 Relationship between phase stability of a two-component mixture and

composition and pressure.

A mixture of components 1 and 2 with composition (z1,z2) between

z1 a and z1 b will be unstable, and will lose
free energy
 by splitting into
phases a and b with compositions z1 ; z1 and z1 ; z1 b respectively.
a a b

Mixtures whose compositions lie in the regions 0 < z1 < z1 a and

z1 b < z1 < 1 will be thermodynamically stable and will not split into
separate phases.
Changes in pressure and temperature of systems will alter the arrange-
ment of molecules, both in the case of pure components and for mixtures.
Because of this, DEmixing and thus free energy as a function of (z1, z2) will
change with pressure and temperature.

PHASE SPLIT FOR TWO-COMPONENT MIXTURES

For a set of different pressures the variation in Gibbs free energy of mixing
(indicated by red broken lines in Fig. A1.3) shows the origin of the
two-phase envelopes we saw with hydrocarbon mixtures.