Chapter 17

Entropy, Free Energy, and Equilibrium

This chapter covers the concepts of entropy and free energy as part of thermodynamics and
relates these concepts to equilibrium. Upon completion of this chapter, your students should be
able to:

1. State the three laws of thermodynamics.

2. Provide several examples of spontaneous processes.
3. Give several examples of endothermic spontaneous processes.
4. Define entropy using the terms disorder or randomness.
5. Justify why entropy of one mole of steam is greater than the entropy of one mole of water.
6. Predict the sign on the change in entropy (∆S) for common processes.
7. Describe what is meant by ∆Suniverse, ∆Ssystem, and ∆Ssurroundings.
8. Relate ∆Suniverse for spontaneous processes and for processes at equilibrium.
9. Use thermodynamic table to determine ∆Sreaction.
10. Mathematically relate ∆Ssurroundings to ∆Hsystem and the temperature.
11. Express Gibbs free energy in terms of H, T, and S.
12. Predict if a reaction is spontaneous, spontaneous in the reverse direction or at equilibrium
from the sign on ∆G.
13. Use thermodynamic tables to determine ∆G of a reaction.
14. Predict the direction of a spontaneous reaction given ∆H, ∆S, and T.
15. Calculate ∆S for phase changes given ∆Hfusion or ∆Hvaporization and the melting and boiling
point temperatures.
16. Mathematically describe ∆G in terms of ∆G°, the gas constant, temperature and the reaction
quotient.
17. Relate ∆G°, and K, equilibrium constant.
18. Calculate K, equilibrium constant, using data from thermodynamic tables.
19. Describe the concept of coupled reactions and discuss the importance of this concept in
biological systems.

Section 17.1 The Three Laws of Thermodynamics

The three laws of thermodynamics are:

a) First Law – conservation of energy.

b) Second Law – entropy of the universe increases for spontaneous reactions and remains
unchanged in equilibrium processes.
c) Third Law – entropy of a pure crystalline substance is zero at absolute zero.
Section 17.2 Spontaneous Processes

Spontaneous reactions can be either exothermic or endothermic; therefore, an additional

thermodynamic parameter is required to predict if a reaction is or is not spontaneous. I liked my
sentence better but it is ok if you want to use yours. That parameter is entropy – a measure of
disorder of a system.

Section 17.3 Entropy

If a state has a low probability of happening, it has small entropy. If a state has a high probability
of happening, it has high entropy. For example, shaking a box full of dominoes and having them
all stand up on end has a very small probability of happening; therefore, the box of dominoes all
standing on end has lower entropy than the same box with the dominoes scattered randomly. It is
noted that entropies of all elements and compounds are all positive which is in contrast to
enthalpies which can be negative, positive, or zero.

Section 17.4 The Second Law of Thermodynamics

∆Suniverse = ∆Ssystem + ∆Ssurroundings > 0 for spontaneous reactions

∆Suniverse = ∆Ssystem + ∆Ssurroundings = 0 for reactions at equilibrium

We can use the tables in Appendix 3 to determine the change in entropy for a reaction in the
same manner that we determined the change in enthalpies. It is important to note that ∆S values
are in J/K · mole and not kJ as ∆H values are.
Since gas molecules are in a much more random state than either solids or liquids, a
reaction that has a net increase in gas molecules will have a ∆S° that is negative. If the number of
gas molecules remains constant in a reaction, then it is difficult to make a general statement
about ∆S°. It is noted that thermodynamics can predict if a reaction is spontaneous, but we must
rely on kinetics to tell us how fast that spontaneous reaction will occur. (See Chapter 13 on
kinetics and related topics).

Section 17.5 Gibbs Free Energy

The thermodynamics function that expresses whether or not a reaction is spontaneous is Gibbs
free energy expression:

G = H – TS

For a system held at constant temperature, the change in Gibbs free energy expression becomes

∆G = ∆H – T∆S

which provides a measure of the system’s ability to do work. If the change in Gibbs free energy
is negative, the reaction is spontaneous as written. If Gibbs free energy is positive, the reaction
written in the reverse direction would be spontaneous. If Gibbs free energy is zero, then the
reaction is at equilibrium. The change in Gibbs free energy can be determined by using the
values found in Appendix 3 in the same fashion as the change in enthalpy or entropy was found.
Since
∆G = ∆H – T∆S

if ∆H is negative and ∆S is positive, the value of ∆G must be negative and the reaction will be
spontaneous. If ∆H is positive and ∆S is negative, the value of ∆G is positive, thus the reaction
would be spontaneous if written in reverse. If both ∆H and ∆S are positive, then ∆G will be
positive if T is small such that the magnitude of T∆S is smaller than ∆H. If both ∆H and ∆S are
negative, ∆ will be negative only if T is small such that the magnitude of T∆S is smaller than ∆H.
If ∆G is zero, then ∆S must equal ∆H/T. Since phase transitions occur at equilibrium and
∆G is zero at equilibrium, it is possible to calculate ∆S for such transitions as ice melting to form
liquid water or liquid water forming steam This is applicable to phase change from solid to liquid
at melting point or liquid to gas at boiling point for any substance.

Section 17.6 Free Energy and Chemical Equilibrium

For the situation where the reaction is not at standard state, we use

∆G = ∆G° + RT lnQ

where Q is the same reaction quotient that we used in determining what direction a reaction
would shift to reach equilibrium. Since both ∆G must be zero and Q must equal K at equilibrium,
it follows that

∆G° = –RT ln K

This is the important reaction that ties thermodynamics and equilibrium constants together. If we
know ∆G°, we can determine K, or if we know K, we can determine ∆G°.

Section 17.7 Thermodynamics in Living Systems

Living systems are extremely complex systems with highly structured parts. For a tree to
combine carbon dioxide and water to form its ordered trunk, ∆S of the system must decrease. At
first glance it would seem that the tree would be violating the laws of thermodynamics because
∆S is negative. However, one must also realize that sunlight is required for that tree to grow and
∆S for the sun is positive, thus the change in entropy for the universe is positive, which is exactly
what the second law states.
Certainly, understanding thermodynamics of simple systems can be confusing; however,
the thermodynamics of biological systems are even more complex.
Chemistry in Action entitled “The Thermodynamics of a Rubber Band” on page 803, it is
pointed out that a rubber band in its natural, un-stretched position has a more disordered state
than when it is stretched. It is though that random intertwining of the polymer molecules is lost
when the rubber is stretched. When the molecules are stretched, they start to align themselves
and can even form small regions where crystallization can take place. This simple demonstration
can be used to introduce an extremely complex phenomena.