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Chemical
Thermodynamics
John D. Bookstaver
St. Charles Community College
St. Peters, MO
2006, Prentice Hall, Inc.
Modified by S.A. Green, 2006
Modified by D. Amuso 2011
Thermodynamics
The study of the relationships between
heat, work, and the energy of a
system.
Entropy
Entropy can be thought of as a
measure of the randomness or disorder
of a system.
It is related to the various modes of
motion in molecules (microstates).
Vibrational
Rotational
Translational
Entropy
Molecules have more entropy (disorder) when:
1)Phase Changes from: S L G
Example: Sublimation
CO2(s) CO2(g)
2)Dissolving occurs (solution forms):
Example:
NaCl(s) Na+(aq) + Cl-(aq)
Entropy
3) Temperature increases
Example:
Fe(s) at 0 oC Fe(s) at 25 oC
4) For Gases ONLY, when
Volume increases or Pressure decreases
Examples:
2 Liters He(g) 4 Liters He(g)
3 atm He(g) 1 atm He(g)
Entropy
5) Rx results in more molecules/moles of gas
Examples:
2NH3(g) N2(g) + 3H2(g)
CaCO3(s) CaO(s) + CO2(g)
N2O4(g) 2 NO2(g)
This one is difficult to predict:
N2(g) + O2(g) 2 NO(g)
Entropy
6) When there are more moles
Example:
1 mole H2O(g) 2 moles H2O(g)
7) When there are more atoms per molecule
Examples:
1 mole Ar(g) 1 mole HCl(g)
1 mole NO2(g) 1 mole N2O4(g)
Entropy
8) When an atom has a bigger atomic
number
1 mole He(g) 1 mole Ne (g)
Spontaneous Processes
Spontaneous processes
are those that can
proceed without any
outside intervention.
The gas in vessel B will
spontaneously effuse into
vessel A, but once the
gas is in both vessels, it
will not spontaneously
move to just one vessel.
Spontaneous Processes
Processes that are spontaneous at one
temperature may be nonspontaneous at other
temperatures.
Above 0C it is spontaneous for ice to melt.
Below 0C the reverse process is spontaneous.
Spontaneous Processes
Processes that are
spontaneous in one
direction are
nonspontaneous in
the reverse
direction.
Spontaneous
processes are
irreversible.
Irreversible (Spontaneous):
Standard Entropies
Standard Conditions:
298 K, 1 atm, 1 Molar
The values for Standard
Entropies (So) are expressed
in J/mol-K.
Note: Increase with
increasing molar mass.
Standard Entropies
Larger and more complex molecules
have greater entropies.
Entropy Changes
So = n Soproducts - mSoreactants
Go = Ho TSo
Use G to decide if a process is spontaneous
G = negative value = spontaneous
G = zero = at equilibrium
G = positive value = not spontaneous
Note: equation can be used w/o the o too.
2. If G is positive
G = minimum amt of work needed
to make the reaction happen
Go = Ho TSo
Go = Ho TSo
In our tables, units are:
Go = kJ/mol
Ho = kJ/mol
So = J/mol-K
At Equilibrium
Go = Ho TSo
Go = zero
Or:
Therefore: Ho = TSo
SoHo
T
Go = n Gof
products
- mGo f
reactants
Go = Ho TSo
Go = RT ln K
Relationships
Go = RT ln K