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Chemical Equilibrium

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

Just because the energy is “there” does not


mean it will be available to do anything useful.
• the sum of the entropy changes of the system
and surroundings determines whether a
process will occur spontaneously
• In chemical thermodynamics focus is on the
attention on the system rather than the
surroundings
• avoid calculatation of the entropy change of
the surroundings explicity
• The free energy enables us to do this for
changes that occur at a constant temperature
and pressure (the Gibbs free energy) or
constant temperature and volume (the
Helmholtz free energy.)
Gibbs Free Energy

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

Under these conditions, both the ΔH and TΔS terms will be


negative, so ΔG will be negative regardless of the temperature.

An exothermic reaction whose entropy increases will be


spontaneous at all temperatures.
Case 2: ΔH < 0 and ΔS < 0

If the reaction is sufficiently exothermic it can force ΔG to be


negative only at temperatures below which |TΔS| < |ΔH|

This means that there is a temperature T = ΔH / ΔS at which


the reaction is at equilibrium; the reaction will only proceed
spontaneously below this temperature. The freezing of a liquid
or the condensation of a gas are the most common examples
of this condition.
Case 3: and ΔS > 0

This is the reverse of the previous case; the entropy increase


must overcome the handicap of an endothermic process so that
TΔS > ΔH.

Since the effect of the temperature is to "magnify" the influence


of a positive ΔS, the process will be spontaneous at
temperatures above T = ΔH / ΔS.
Think of melting and boiling
Case 4: and ΔS < 0

With both ΔH and ΔS working against it, this kind of process will
not proceed spontaneously at any temperature.

Substance A always has a greater number of accessible energy


states, and is therefore always the preferred form.
The Gibbs energy is the maximum useful work
(excluding PV work associated with volume
changes of the system) that a system can do on
the surroundings when the process occurs
reversibly at constant temperature and
pressure.
Defining ΔG° and ΔGf°

Recall that the symbol ° refers to the standard


state of a substance measured under the
conditions of 1 atm pressure or an effective
concentration of 1 mol L–1 and a temperature of
298K.
standard free energy of formation

ΔGf° = ΔHf° – TΔSf°(4-6)

standard Gibbs energy of the reaction


according to

ΔG° = Σ ΔGf°(products)– Σ ΔGf°(reactants)


Problem Example 1

Find the standard Gibbs energy change for the reaction


CaCO3(s) → CaO(s) + CO2(g)
The ΔGf° values for the three components of this reaction
system are CaCO3(s): –1128 kJ mol–1, CaO(s): –
603.5 kJ mol–1, CO2(g): –137.2 kJ mol–1.
Solution

Substituting into ΔG° = Σ ΔGf°(products)– Σ ΔGf°(reactants),


ΔG° = (–603.5 –137.2) – (–1128) kJ mol–1 = +130.9 kJ mol–1
indicating that the process is not spontaneous under
standard conditions (i.e., solid calcium carbonate will not
form solid calcium oxide and CO2 at 1 atm partial pressure
at 25° C.
The practical importance of the Gibbs energy is that it
allows us to make predictions based on the properties (ΔG°
values) of the reactants and products themselves,
eliminating the need to experiment

But bear in mind that while thermodynamics always


correctly predicts whether a given process can take place (is
spontaneous in the thermodynamic sense), it is unable to
tell us if it will take place at an observable rate.

When thermodynamics says "no", it means exactly that.


When it says "yes", it means "maybe".
ΔG and ΔG°: what's the difference?
Although it is ΔG rather than ΔG° that serves as a
criterion for spontaneous change at constant
temperature and pressure, ΔG° values are so
readily available that they are often used to get a
rough idea of whether a given chemical change is
possible. This is practical to do in some cases, but
not in others.
the standard free energy change ΔG° has a single value for a
particular reaction at a given temperature and pressure

this is the difference (ΣG°f, products – ΣG°f, reactants)


that you get from tables.

It corresponds to the free energy change for a process that


never really happens: the complete transformation of pure
N2O4 into pure NO2 at a constant pressure of 1 atm.

The other quantity ΔG represents the total free energies of


all substances in the reaction mixture at any particular
system composition.
Finding the equilibrium temperature
A reaction is in its equilibrium state when
ΔG = ΔH – TΔS = 0
The temperature at which this occurs is given by
T = ΔH / TΔS

If we approximate ΔH by ΔH° and ΔS by ΔS°, we can estimate


the normal boiling point of a liquid. From the following
thermodynamic data for water:
we find that liquid water is in equilibrium with water vapor
at a partial pressure of 1 atm when the temperature is

T = (44100 J) / (118.7 J K–1) = 371.5 K


The road to equilibrium is down the
free energy hill
• if the total free energy G of a mixture of reactants
and products goes through a minimum value as
the composition changes, then all net change will
cease— the reaction system will be in a state of
chemical equilibrium
• the relative concentrations of reactants and
products in the equilibrium state is expressed by
the equilibrium constant
• examine the relation between the Gibbs free
energy change for a reaction and the equilibrium
constant
To keep things as simple as possible, we will consider a
homogeneous chemical reaction of the form
A + B→ C + D
In order to understand how equilibrium constants relate to
ΔG° values, assume that all of the reactants are gases, so
that the free energy of gas A, for example, is given at all
times by

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)

We can now express the G° terms collectively as ΔG°, and


combine the logarithmic pressure terms into a single
fraction
𝑃𝐶 𝑃𝐷
∆𝐺 = ∆𝐺° + 𝑅𝑇𝑙𝑛
𝑃𝐴 𝑃𝐵
which is more conveniently expressed in terms of the
reaction quotient QP

ΔG = ΔG° + RT ln Q

The free energy G is a quantity that becomes more


negative during the course of any natural process.
ΔG° is a constant for a given reaction

ΔG varies continuously as the composition changes, finally


reaching zero at equilibrium

ΔG is the “distance” (in free energy) from the equilibrium


state of a given reaction.
Recall ΔG = ΔG° + RT ln Qp
• As the reaction approaches equilibrium, ΔG
becomes less negative and finally reaches zero.
• At equilibrium ΔG = 0 and Q = K, so we can write
ΔG° = –RT ln Kc
• in which Kc, the equilibrium constant expressed in
pressure units, is the special value of Q that
corresponds to the equilibrium composition.

−∆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