Chemical Thermodynamics

Spontaneous Process
 processes or reaction that proceed on their own in a definite direction, without any
outside intervention
 go to completion even without further input of energy once started
 usually irreversible, occurs slowly or instantaneously
 includes nearly all exothermic changes

Entropy
 a measure of the randomness or disorder of a system
 the greater the degree of disorder, the greater the entropy
 degree of disorder in matter depends on its phase or physical state

Factors Affecting Entropy

 Changes in Phase - entropy increases as the solid changes to liquid, and liquid
vaporizes into gas
 Change in Temperature - increase in temperature = increased molecular movement =
more disorderly state
 Number of Particles - “the more, the merrier”, an increase in number of particles
increases entropy

The Second Law of Thermodynamics

 The total entropy of the universe is continually increasing.
 ∆Suniverse = ∆Ssystem + ∆Ssurroundings
 Spontaneous processes continuously occur in energy-rich universe.

Gibbs Free Energy (G)

 portion of energy change in spontaneous reactions that is available to do useful work
 maximum amount of work that can be done
 G = H - TS
 where H = enthalpy, T = Kelvin temperature and S = entropy

 For a process occurring at constant temperature, the chang in free energy of the
system is
 ∆G = ∆H - T∆S
 If both temperature and pressure are constant, the relationship between
the sign of ∆G and spontaneity of a reaction is as follows:
 ∆G < 0, reaction is spontaneous and in the forward direction
 ∆G > 0, reaction is nonspontaneous in the forward direction, work
must be supplied to make it occur
 ∆G = 0, reaction is ar equilibrium