- Physical Chemistry I
Spring 2013 Unique 52575
Lecture Summary, 2 February 2013
Law of Thermodynamics: We have already seen that the
second law of thermodynamics defines the direction of spontaneous
change of a thermodynamic process. However, in order to apply
this, we have to know the total change in entropy of the
universe, not just the change in entropy of our system:
deltaS(tot) = deltaS(sys) + deltaS(surr) >= 0
The equality applies of the process is reversible, the inequality applies in all other cases. This means that we have to determine not only the entropy change of the system but also of the surroundings. Our rules for solving entropy problems are:
1. For any reversible process, deltaS(tot) = 0
2. To find deltaS(sys), use a reversible path from initial to final states. You can do this because entropy is a state function and doesn't depend on the actual path.
3. Determine deltaS(surr) independently. If the process is reversible, you already know deltaS(surr) = -deltaS(sys). If the process is irreversible, deltaS(surr) = q(surr)/T, and you will have to figure out what q(surr) is.