Law of Thermodynamics
Spontaneous Processes
Entropy
The Carnot Heat Engine
The Second Law of Thermodynamics
The Third Law of Thermodynamics
Gibbs Free Energy
Gibbs and Helmholtz Energies and its
Applications
Spontaneous Process
In terms of chemical reaction:
- We consider exothermic and endothermic
reactions,
- exothermic reaction seems to favor
spontaneity while endothermic reaction is not
Some spontaneous process (conversion of
diamond to graphite) maybe so slow that the
tendency never realized in practice.
Thus, in order to determine the spontaneity of a
reaction, we need another term called
ENTROPY (S)
Spontaneous Process
A reaction that does occur in a given set of
conditions spontaneous reaction
A reaction that does not occur under specified
conditions non-spontaneous reaction
Examples:
A waterfall runs downhill but never up,
spontaneously
Water freezes below 0C and ice melts
above 0C, spontaneously (at 1 atm)
Heat flows from hotter object to colder one,
but reverse never happens spontaneously
Iron exposed to water and oxygen forms
rust, but rust does not change back to iron
spontaneously
What determines
reaction of
spontaneous
change?
Entropy, S
Entropy is often described as a measure on how
disperse or spread out the energy of a system among
the different possible ways that a system can contain
energy
The GREATER the dispersal of energy the GREATER
the entropy of a system
A system that spread to lower microstates has lower
entropy
A system that spread to higher microstates has higher
entropy
Spontaneous Process
Consider a cup of hot coffee:
Has a certain amount of entropy due to the
dispersal among the various energy states of
water molecules (vibrate, rotate,etc.)
Various energy states/dispersal of energy
known as MICROSTATES
> microstates , > entropy
Microstates increase with temperature
(i.e. more vibration and more rotation of
molecules)
Spontaneous Process
Example:
Calculate the entropy change of a
sample of perfect gas when it expands
isothermally from a volume Vi to a
volume Vf.
Surroundings
Example:
Entropy change
Gibbs Energy
Gibbs Energy