Chapter 19
Chemical Thermodynamics
Thermodynamics
The study of the relationships between
heat, work, and the energy of a
system.
First Law of
Thermodynamics
You will recall from Chapter 5
that energy cannot be created
nor destroyed.
Therefore, the total energy of
the universe is a constant.
Energy can, however, be
converted from one form to
another or transferred from a
system to the surroundings or
vice versa.
Second Law of
Thermodynamics
The total Entropy of the universe
increases in any spontaneous,
irreversible process.
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:
Entropy
2 Liters He(g) 4 Liters He(g)
Entropy can be thought of as a
measure of the randomness or
disorder of a system.
3 atm He(g) 1 atm He(g)
It is related to the various
modes of motion in molecules
(microstates).
Vibrational
Entropy
5) Rx results in more molecules/moles
of gas
Examples:
2NH3(g) N2(g) + 3H2(g)
Rotational
Translational
CaCO3(s) CaO(s) + CO2(g)
N2O4(g) 2 NO2(g)
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
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 in one
direction are nonspontaneous in the
reverse direction.
Spontaneous processes are
irreversible.
Second Law of
Thermodynamics
A reversible process results in
no overall change in Entropy while an
irreversible, spontaneous process
results in an overall increase in
Entropy.
Third Law of
Thermodynamics
The Entropy of a pure crystalline
substance at absolute zero is zero.
why?
Third Law of
Thermodynamics
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.
There are two parts to the free
energy equation:
H the enthalpy term
TS the entropy term
Standard Entropies
Larger and more complex molecules
have greater entropies.
The temperature
dependence of free
energy comes from the
entropy term.
What causes a reaction to
be spontaneous?
DSo = S n Soproducts - S m Soreactants
Think Humpty Dumpty
Gibbs Free Energy
System tend to seek:
Gibbs Free Energy
Entropy Changes
Minimum Enthalpy
Exothermic Rx, DH = negative
1. If DG is negative
DG = maximum amt of energy
free to do
work by the reaction
Maximum Entropy
More disorder, DS = positive
Because: DGo = DHo TDSo
2. If G is positive
DG = minimum amt of work
needed
to make the reaction
happen
Gibbs Free Energy
Free Energy and
Temperature
At Equilibrium
DGo = zero
TDSo
In our tables, units are:
Or:
DGo = kJ/mol
DHo = kJ/mol
DSo = J/mol-K
Free Energy and Temperature
= (-)
(+)
Therefore: DHo =
DSo = DHo
T
Use this equation when asked to
calculate enthalpy of vaporization or
enthalpy of fusion.
Standard Free Energy
Changes
Be careful: Values for Gf are in
kJ/mol
Free Energy and Equilibrium
Remember from above:
If DG is 0, the system is at
equilibrium.
So DG must be related to the
equilibrium constant, K (chapter 15).
The standard free energy, DG, is
directly linked to Keq by:
Where R = 8.314 J/molK
DGo = - RT ln K
If the free energy change is a
negative value,
the reaction is spontaneous, ln
K must be a positive value, and
K will be a large number
meaning the equilibrium
mixture is mainly products.
If the free energy change is
zero,
ln K = zero and K = one.
Free Energy and Equilibrium
DGo = - RT ln K
Relationships
Under non-standard conditions, we
need to use DG instead of DG.
