Spontaneity of Chemical Reactions

One might be tempted based on the results of thermochemistry

to predict that all exothermic reactions would be spontaneous.
The corollary this would be the statement that no endothermic
reactions are spontaneous. However, this is not the case. There
are numerous examples of endothermic reactions that are
spontaneous. Of course, heat must be taken up from the
surroundings in order for such processes to occur. Nonetheless,
the enthalpy of the reaction does not determine whether or not
the reaction will occur, only how much heat will be required or
generated by the reaction. The observation that gases expand
to fill a vacuum and that different substances spontaneously mix
when introduced into the same vessel are further examples that
require quantitative explanation.
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
Spontaneous Processes

Processes that are

spontaneous in one
direction are
nonspontaneous in
the reverse direction.
Spontaneous Processes
 Processes that are spontaneous at one temperature
may be nonspontaneous at other temperatures.
 Above 0C it is spontaneous for ice to melt.
 Below 0C the reverse process is spontaneous.
Reversible Processes

In a reversible process
the system changes in
such a way that the
system and
surroundings can be
put back in their
original states by
exactly reversing the
process.
Irreversible Processes

 Irreversible processes cannot be undone by

exactly reversing the change to the system.
 Spontaneous processes are irreversible.
 Entropy

 Entropy (S) is a term coined by Rudolph

Clausius in the 19th century.
 Clausius was convinced of the significance
of the ratio of heat delivered and the
temperature at which it is delivered,
q
T
 Entropy

 Entropy can be thought of as a measure of

the randomness of a system.
 It is related to the various modes of motion
in molecules.
 Entropy

 Like total energy, E, and enthalpy, H, entropy

is a state function.
 Therefore,
S = Sfinal  Sinitial
 Entropy

 For a process occurring at constant temperature

(an isothermal process), the change in entropy is
equal to the heat that would be transferred if the
process were reversible divided by the
temperature:

qrev
S =
T
Second Law of Thermodynamics
The second law of thermodynamics states
that the entropy of the universe increases
for spontaneous processes, and the
entropy of the universe does not change
for reversible processes.
Second Law of Thermodynamics
In other words:
For reversible processes:
Suniv = Ssystem + Ssurroundings = 0
For irreversible processes:
Suniv = Ssystem + Ssurroundings > 0
Second Law of Thermodynamics
These last truths mean that as a result of
all spontaneous processes the entropy of
the universe increases.
Calculating reversible irreversible paths
System and surroundings
Understanding the irreversible
path
The dependence of the entropy on volume
The dependence of the entropy on temperature
Summary of entropy calculations
Entropy of mixing
The Third Law of
Thermodynamics
 The third law of thermodynamics states that every substance has a positive
entropy, but at zero Kelvin the entropy is zero for a perfectly crystalline
substance. The third law introduces a numerical scale for the entropy. Stated
succinctly:

S(0) = 0 for all perfectly ordered crystalline materials.

It is commonly said that all motion ceases at absolute

zero. Certainly all translation and rotation have ceased
at absolute zero. However, the nuclei still vibrate about
their equilibrium positions in so-called zero point motion.
However, all molecules are in their lowest vibrational
state and entropy is zero in any case provided there are
no imperfections in the crystal.
 Residual Entropy
The first statistical picture of entropy was that of Boltzmann.
The function W that represents the number of ways we can distribute N
particles into a number of states. Using the function W the entropy can be
expressed as:

S = kB ln W

At zero Kelvin the system is in its lowest energy state. For a perfect crystal
there is only one way to distribute the energy and W = 1, therefore S = 0.
However, the entropy not equal to zero at T = 0 K if the substance is not a
perfect crystal. Although the residual entropy in such cases is a small
correction to the entropy calculated for chemical reactions it still leads to an
important concept.
 Hitung entropi 1 mol CO(s) pada T=0K
pada satu jenis orientasi bentuknya, jika
setiap molekul CO dapat membentuk 2
orientasi bentuk yang keduanya tidak
mempengaruhi entropinya
 CO: an Imperfect Crystal
The molecule CO has a very small dipole moment and there is a finite chance that CO
will crystallize as CO:CO:CO instead of CO:OC:CO. For each CO molecule there are
two possible orientations of the molecule, therefore there are two ways each CO can
exist in the lattice. The number of ways per molecule is w = 2 for each CO. If we have N
CO molecules there are wN ways or 2N ways that all of the CO can be distributed.
Therefore, the entropy at zero Kelvin is

The entropy at zero Kelvin is known as residual entropy. There are number of
substances that show similar statistical variations in orientation that lead to a residual
entropy.