Spontaneity: Entropy and Free Energy

Second Law of Thermodynamics

The total entropy of the universe increases when a spontaneous event occurs. Relates enthalpy change, entropy change, and temperature as the three factors that influence spontaneity.

Third Law of Thermodynamics

At absolute zero, the entropy of a perfectly ordered pure crystalline substance is zero. Kind of useless since we rarely see perfect crystals or achieve absolute zero. Totally useful in that we can experimentally determine entropy values at temperatures above absolute zero. So, what is entropy anyway?

Entropy (S)
Is a measure of the disorder of a system Is a state function Related to possibilities for energy distribution Usually has units of J/Kmol NOT kJ
They are trying to trick us. Do not let them!

Is better represented as S, which is the change in entropy + S = increasing disorder (chaos)

This is favored. Nature is lazy and also likes chaos. Sort of like a teenage girl*.

- S = decreasing disorder (organization) *Excluding teenage girls enrolled in AP Chemistry

In English, Please
Its like this: if energy were money, entropy would describe the number of different ways of counting it out. Using American paper money, I can count out $2 in two ways: 2 $1 bills or 1 $2 bill Using American coins, I can count out $2 in several ways: 4 half dollars, 8 quarters, 20 dimes, four quarters and two half dollars, etc. The system using coins has more entropy than the system using paper money.

In Chemical Terms, Please

Factor Volume of gas increases Temperature increases State of matter Pure solids or liquids dissolving in a solvent Number of particles increases Effect on Entropy Increases Increases Solids<liquids<gases Increases (unless its a carbonate) Increases

S = S(products) - S(reactants) Look familiar? Appendix L of text.

Examples
Predict the algebraic sign of S for the reactions:
2NO2 (g) N2O4 (g) C3H8 (g) + 5O2 (g) 3CO2 (g) + 4H2O (g)

Examples
Calculate the S for the oxidation of NO with O2. 2NO (g) + O2 (g) 2NO2 (g)

Homework
Pgs. 934-935 #1, 3, 5, 7, 9, 11