Chapter 19

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.

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
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.

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.
Reversible:

Irreversible (Spontaneous):

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.

Standard Entropies
Larger and more complex molecules
have greater entropies.

Entropy Changes
So = n Soproducts - mSoreactants

Be careful: Sunits are in J/mol-K

Note for pure elements:

Gibbs Free Energy

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.

Gibbs Free Energy

1. If G is negative
G = maximum amt of energy free to do
work by the reaction

2. If G is positive
G = minimum amt of work needed
to make the reaction happen

Go = Ho TSo

Gibbs Free Energy

Go = Ho TSo
In our tables, units are:
Go = kJ/mol
Ho = kJ/mol
So = J/mol-K

Free Energy and Temperature

There are two parts to the free energy
equation:
H the enthalpy term
TS the entropy term

The temperature dependence of free

energy comes from the entropy term.

What causes a reaction to be

spontaneous?
Think Humpty Dumpty
System tend to seek:
Minimum Enthalpy
Exothermic Rx, H = negative
Maximum Entropy
More disorder, S = positive
Because: Go = Ho TSo
- = (-) - (+)

Free Energy and Temperature

By knowing the sign (+ or -) of S and H,

we can get the sign of G and determine if a
reaction is spontaneous.

At Equilibrium

Go = Ho TSo
Go = zero
Or:

Therefore: Ho = TSo
SoHo
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

Go = n Gof

products

- mGo f

reactants

G can be looked up in tables or calculated

from S and H.

Go = Ho TSo

Free Energy and Equilibrium

Remember from above:
If G is 0, the system is at equilibrium.
So G must be related to the equilibrium constant, K (chapter
15). The standard free energy, G, is directly linked to
Keq by:

Go = RT ln K

Where R = 8.314 J/mol-K

Relationships

Go = 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

Under non-standard conditions, we need to use
G instead of G.

Q is the reaction quotient from chapter 15.