Chap19_CHE1402_slides(1).ppt of coursecs

Chapter 19
Chemical
Thermodynamics

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.

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
return to vessel B.

Processes that are
spontaneous in one
direction are
nonspontaneous in
the reverse
direction.

• 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:
S =
qrev
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.

In other words:
For reversible processes:
Suniv = Ssystem + Ssurroundings = 0
For irreversible processes:
Suniv = Ssystem + Ssurroundings > 0

These last truths mean that as a result
of all spontaneous processes the
entropy of the universe increases.

Entropy on the Molecular Scale
• Ludwig Boltzmann described the concept of
entropy on the molecular level.
• Temperature is a measure of the average
kinetic energy of the molecules in a sample.

• Molecules exhibit several types of motion:
– Translational: Movement of the entire molecule from
one place to another.
– Vibrational: Periodic motion of atoms within a molecule.
– Rotational: Rotation of the molecule on about an axis or
rotation about  bonds.

• Boltzmann envisioned the motions of a sample of
molecules at a particular instant in time.
– This would be akin to taking a snapshot of all the
molecules.
• He referred to this sampling as a microstate of the
thermodynamic system.

• Each thermodynamic state has a specific number of
microstates, W, associated with it.
• Entropy is
S = k lnW
where k is the Boltzmann constant, 1.38  1023
J/K.

• The change in entropy for a process,
then, is
S = k lnWfinal  k lnWinitial
lnWfinal
lnWinitial
S = k ln
• Entropy increases with the number of
microstates in the system.

• The number of microstates and,
therefore, the entropy tends to increase
with increases in
– Temperature.
– Volume.
– The number of independently moving
molecules.

Entropy and Physical States
• Entropy increases with
the freedom of motion
of molecules.
• Therefore,
S(g) > S(l) > S(s)

Solutions
Generally, when
a solid is
dissolved in a
solvent, entropy
increases.

Entropy Changes
• In general, entropy
increases when
– Gases are formed from
liquids and solids;
– Liquids or solutions are
formed from solids;
– The number of gas
molecules increases;
– The number of moles
increases.

Third Law of Thermodynamics
The entropy of a pure crystalline
substance at absolute zero is 0.

Standard Entropies
• These are molar entropy
values of substances in
their standard states.
• Standard entropies tend
to increase with
increasing molar mass.

Standard Entropies
Larger and more complex molecules have
greater entropies.

Entropy Changes
Entropy changes for a reaction can be
estimated in a manner analogous to that by
which H is estimated:
S = nS(products) — mS(reactants)
where n and m are the coefficients in the
balanced chemical equation.

Entropy Changes in Surroundings
• Heat that flows into or out of the
system changes the entropy of the
surroundings.
• For an isothermal process:
Ssurr =
qsys
T
• At constant pressure, qsys is simply
H for the system.

Entropy Change in the Universe
• The universe is composed of the system
and the surroundings.
• Therefore,
Suniverse = Ssystem + Ssurroundings
• For spontaneous processes
Suniverse > 0

Entropy Change in the Universe
• Since Ssurroundings =
and qsystem = Hsystem
This becomes:
Suniverse = Ssystem +
Multiplying both sides by T, we get
TSuniverse = Hsystem  TSsystem
Hsystem
T
qsystem
T

Gibbs Free Energy
TSuniverse is defined as the Gibbs free
energy, G.
• When Suniverse is positive, G is
negative.
• Therefore, when G is negative, a
process is spontaneous.

Gibbs Free Energy
1. If G is negative, the
forward reaction is
spontaneous.
2. If G is 0, the system
is at equilibrium.
3. If G is positive, the
reaction is
spontaneous in the
reverse direction.

Standard Free Energy Changes
Analogous to standard enthalpies of
formation are standard free energies of
formation, G.
f
G = nG (products)  mG (reactants)
f f
where n and m are the stoichiometric
coefficients.

Free Energy Changes
At temperatures other than 25°C,
G° = H  TS
How does G change with temperature?

Free Energy and Temperature
• There are two parts to the free energy
equation:
 H— the enthalpy term
– TS — the entropy term
• The temperature dependence of free
energy, then comes from the entropy
term.

Free Energy and Equilibrium
Under any conditions, standard or
nonstandard, the free energy change
can be found this way:
G = G + RT lnQ
(Under standard conditions, all concentrations are 1 M,
so Q = 1 and lnQ = 0; the last term drops out.)

Free Energy and Equilibrium
• At equilibrium, Q = K, and G = 0.
• The equation becomes
0 = G + RT lnK
• Rearranging, this becomes
G = RT lnK
or,
K = e
-G
RT

• How do cations tend to change the pH
when they are introduced in water ?
• How do anions tend to change the pH when
they are introduced in water ?
• What is the relationship between Ka and
Kb ? Justify by using the couple HF/F-
.
POP QUIZ !
POP QUIZ !

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