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Reference: http://www.chem1.com/acad/webtext/thermeq/TE4.html
the central purpose of chemical
thermodynamics
• The purpose of thermodynamics is to predict
the equilibrium composition
of a system from the properties of its
components.
What is a spontaneous process?
A non-spontaneous process
For all spontaneous processes
• Once they are allowed to commence, they will
proceed to the finish without any outside
intervention.
• It would be inconceivable that any of these
changes could occur in the reverse direction
(that is, be undone) without changing the
conditions or actively disturbing the system in
some way.
• The direction of a spontaneous process is not
governed by the energy change...
• ... and thus the First Law of Thermodynamics
cannot predict the direction of a natural
process.
When a chemical reaction takes place, two kinds of
changes relating to thermal energy are involved:
• The ways that thermal energy can be stored within
the reactants will generally be different from those
for the products.
H2 → 2 H
When a chemical reaction takes place, two kinds
of changes relating to thermal energy are
involved:
• In order for this dissociation to occur,
however, a quantity of thermal energy (heat)
q = ΔU must be taken up from the
surroundings in order to break the H–H bond.
All molecules spontaneousy absorb
heat and dissociate at high
temperatures.
LeChâtelier Principle
the equilibrium state for an endothermic
reaction is shifted to the right at higher
temperatures.
• Spontaneous change is that which, once initiated,
proceeds on its own until some state of equilibrium
(mechanical, thermal, chemical, etc.) is attained.
• All natural processes (those that occur in the
world) ultimately involve spontaneous change.
• Thermal energy is kinetic energy associated with
the random motions of atoms and molecules.
These states of motion are quantized into energy
states which can be realized in huge numbers of
different ways that we call microstates.
• All microstates are equally probable, but only those
whose energy levels are commensurate with the
available thermal energy as determined by the
temperature will be thermally accessible and likely
to be populated.
• Spontaneous change is driven by the tendency of
thermal energy to spread into as many microstates
of the system and surroundings as are thermally
accessible.
entropy
recall that the First Law of thermodynamics,
expressed as ΔU = q + w, is essentially a
statement of the law of conservation of
energy. The significance of this law is that it
tells us that any proposed process that would
violate this condition can be dismissed as
impossible, without even inquiring further
into the details of the process.
• The second law of thermodynamics says in
effect, that the extent to which any natural
process can occur is limited by the dilution of
thermal energy (increase in entropy) that
accompanies it, and once the change has
occurred, it can never be un-done without
spreading even more energy around.
A more brief statement of the Second
Law
The entropy of the world only increases and
never decreases.
important consequence of the Second
Law
G=H–TS
ΔG = ΔH – TΔStotal
ΔStotal = ΔSsurr + Δssys
–qp / T = –ΔH/T
ΔStotal = (– ΔH/T) + ΔSsys
TΔStotal = – ΔH +T ΔSsys
Gibbs energy and chemical change
• In a spontaneous change, Gibbs energy
always decreases and never increases.
• the entropy of the world behaves in the exact
opposite way (owing to the negative sign in
the TΔS term)
H2O(liquid) → H2O (ice)
summary
reaction can spontaneously proceed to the
ΔG < 0
right: A → B
reaction can spontaneously proceed to the
ΔG > 0
left: A ← B
the reaction is at equilibrium; the quantities of A
ΔG = 0
and B will not change
• condition for spontaneous change
ΔG = ΔH – TΔS < 0
Case 1: ΔH < 0 and ΔS > 0
With both ΔH and ΔS working against it, this kind of process will
not proceed spontaneously at any temperature.
GA = GA° + RT ln PA
The free energy change for the reaction is sum of the free
energies of the products, minus that of the reactants:
ΔG = GC + GD – GA – GB
Using the first equation to expand each term on the right,
we have
ΔG = (G°C + RT ln PC) + (G°D + RT ln PD) – (G°B + RT ln PB) –
(G°A + RT ln PA)
ΔG = ΔG° + RT ln Q
−∆𝐺°
𝐾 = 𝑒𝑥𝑝
𝑅𝑇
Recall that changing the temperature will increase or
decrease the tendency for a process to take place,
depending on the sign of ΔS°.
This relation can be developed formally by differentiating
the relation
ΔG ° = ΔH ° – TΔS°
with respect to the temperature:
𝑑 −∆𝐺°
= −∆𝑆°
𝑑𝑇
so the sign of the entropy change determines whether the
reaction becomes more or less allowed as the temperature
increases.
• We often want to know how a change in the
temperature will affect the value of an equilibrium
constant whose value is known at some fixed
temperature. Suppose that the equilibrium constant
has the value K1 at temperature T1 and we wish to
estimate K2 at temperature T2. Expanding Eq. 5-7 in
terms of ΔH° and ΔS°, we obtain
–RT1 ln K1 = ΔH ° – T1 ΔS°
and
–RT2 ln K2 = ΔH ° – T2 ΔS°
• Dividing both sides by RT and subtracting, we
obtain
∆𝐻° ∆𝐻°
𝑙𝑛𝐾1 − 𝑙𝑛𝐾2 = − −
𝑅𝑇1 𝑅𝑇2
• Which is most conveniently expressed as the
ratio
𝐾1 ∆𝐻° 1 1
𝑙𝑛 =− −
𝐾2 𝑅 𝑇1 𝑇2