Why does lowering the partial pressure of a product allow

for chemical equilibrium to be achieved in an endothermic

reaction?
Take the case of the isomerization reaction involving hydrogen cyanide and
hydrogen isocyanide
:

HCN HNC
which is described by the potential curve below:

The two compounds are separated by a significant barrier, E a, so that if RT<<Ea, the
high energy isocyanide (HNC) is kinetically stable, and observable as a distinct
chemical species (as opposed to just being a transient location on the internal
rotation path of the CN moiety in the absence of such a barrier). We make the
approximation that So 0 because the molecules are so similar (same stiffness of
vibrations, no bond breaking, etc.). We note that in this case the energetics are also
simple with H0 D, the difference in mechanical potential energy between the two
isomers at their minima along the reaction coordinate. This follows from the rule
that H = U + ngRT and ng = 0 (ng represents the number of gas phase
molecules in the reactants or products), and U is dominated by the potential
energy difference. Putting this together:

G0 = D.
Using our derivation of the Law of Mass Action, we know that the stable partial
pressures of HCN and HNC at equilibrium are governed by:
Keq(T) = PHNC/PHCN = e-(Go/RT) = e-(D/RT)
where the Pi values are in units of the standard state pressure, p ref = 1 atm, (pHCN/pref
PHCN), and pi is a real pressure in atm. If the HCN is held at 1 atmosphere, PHCN =
1, and then the partial pressure of the product is exponentially dependent on the
temperature:
PHNC = e-(D/RT)

[1]

This is a very typical situation for the presence of higher energy species in
thermodynamics, where their relative abundances are governed by an e-(E/RT)
term, usually called the Boltzmann factor. The Maxwell-Boltzmann kinetic energy
distribution (Probability(KE) e-(KE/RT) was already an example of this
phenomenon, which we encountered earlier when discussing the kinetic theory of
gases, but did not derive at that time).

Analysis of chemical equilibrium from the entropy

perspective
We now want to go back to basics and understand the factors that are
responsible for this exponential behavior of the equilibrium partial pressure, and in
the process emphasize that it is all a consequence of the second law and the rules
of heat transfer. The second law has to do with the total change in entropy of
everything, system and surroundings:
Stot = Ssys + Ssurr

[2]

For a chemical reaction, Ssys is Srxn. To be spontaneous, Stot > 0 by the second
law. A reaction is reversible, which is to say at equilibrium, when Stot = 0. Think of
this like the reaction is paying for the heat it needs with currency that has the
value of entropy changes (J/K). An endothermic reaction draws heat, q (=H), out
of the surroundings like a cash transaction at an ATM machine. The act of transfer
changes the surroundings. Pushing ATM analogy, there is less cash in the machine
when you got yours; it does not have an infinite amount of it and cant make new
cash on the spot! If the surroundings were a large water bath, the water is now
different after the withdrawal, slightly cooler. The water is different even though
the bath was so huge that the temperature remained almost invariant during the
transfer, as is required in order that we could claim the reaction occurred at
constant T.*

So something changed when heat came out of the water bath, and the
amazing thing is that the cost of this heat withdrawal is Ssurr = -q/T, no matter
what it came from or how big it was!! If the bath was small, each water in it
changed a lot. If it was large, each constituent only changed a tiny bit. The overall
effect on the bath entropy is q/T either way. In our case,
Ssurr = -D/T.
If the reaction we are carrying out with this heat does not somehow create new
entropy, at least as big as this negative Ssurr above, to compensate, it cannot occur
spontaneously. But should the reaction create more entropy than needed so that:
Stot = Srxn D/RT > 0,

[3]

it will occur spontaneously. In fact, we can say that it has access to free energy
because its entropy production, Srxn, would allow even more heat (D + qfree) to be
withdrawn from the surroundings before the process is shut down by the second law
when:
Stot = Srxn (D + qfree)/RT < 0.
*This is required here because we want to connect with Gibbs free energy stuff above,
where we are obliged to keep T and P constant. The entropy rules do not care about Gibbs,
and Eq. [2] rules the heat cost no matter what.

Also note that when a reaction occurs spontaneously, the resultant Stot(forward) >
0. Could it go back after making this spontaneous change? For this reverse
process:
Stot(backward) = -Stot(forward)
and Stot(backward) < 0. It cannot go back; the reverse reaction is impossible by
the second law. Forward spontaneous reaction is thus irreversible.
Equilibrium occurs when reactions can go forwards and backwards in dynamic
balance, and that can only occur when
Stot(forward) = -Stot(backward) = 0,
the usual condition for a reversible process. Note that when Stot = 0, the entropy
cost of the heat demanded by the reaction is exactly compensated by the entropy
generated by the reaction, and it is intimately in tune with its own heat demand.
When it is out of tune, the reaction process is either impossible or occurs
irreversibly. It is exactly this balance, when the local entropy demanded for a
change is exactly compensated by the entropy change inflicted on the
surroundings, that allowed us to measure the entropy change using Ssys = dqrev/T.

It had to be reversible in order for us to find out Ssys using the change in the
surroundings, because only then are these quantities equal and opposite!
All this means that we can mathematically tune the reaction entropy to find the
equilibrium condition without ever appealing to the Gibbs equation.

Finding entropy by adjusting partial pressures

If a reaction, like the isomerization we are analyzing, cannot generate any
entropy when a given pressure of HCN is converted to the same pressure of HNC,
we can ask what a reaction can do to generate some of the entropy it is missing . It
either gets more S than D/T (Eq. 3) or its no-go. When we have gas phase
species, we already found that the act of expanding a gas at constant temperature
was a great source of entropy, and in fact, analysis of that process was how the
entropy state function was identified in the first place! But how could we take
advantage of this entropy source arising from expansion of gaseous reactants or
products when they are held in the same volume (i.e, the reaction vessel)? This is
where it is useful to remember that entropy is a state function. Using Hesss law,
we can then analyze the consequences of carrying out a reaction with reactants at
one partial pressure to products at another partial pressure in the context of
increased available volume, which we are sure creates entropy.
To see this, consider a very large volume, V2, which is hundreds of times
larger than the molar volume, V1 (22.4 L at STP). The chamber is held against a
heat bath (surroundings) to maintain the temperature. Then fill up this entire
volume with HCN at 1 atm., which represents the reactant in its standard state. Now
consider carrying out the reaction in two steps. In step 1, only the HCN molecules
in the smaller volume V1 (say surrounded by an imaginary membrane that isolates
them within the big chamber) are completely converted to HNC products, which will
clearly also be at 1 atm. Thus 1 mole of HCN has converted to HNC. The imaginary
barrier holding them in V1 has no net pressure on it since the pressure is the same
inside and out. The entropy change for this process is just the Sorxn from above:
S1(rxn) = Sorxn = 0
But the heat bath had to supply the heat demand, D, required to carry out the
reaction, and so step 1 also has a pretty negative contribution,
S1(surr) = -D/T
and therefore
S1(tot) = -D/T.
This would clearly not be spontaneous. Now lets consider a second step (2), where
the imaginary barrier is suddenly removed around the newly formed HNC gas at 1

atm, allowing it to spontaneously fill up the large volume V 2. It does not matter that
HCN is already in this outer region, as the entropy change for HNC is not dependent
on anything going on with HCN. It is true that the HCN initially left outside V 1 will fill
up the tiny (relative) volume V1, and thus also slightly expand, but we can make
this effect as small as we want by making V2 very large.
The entropy change for the HNC in going from V 1 to V2 is just the same as we
calculated before in class for volume changes in the isothermal leg of the Carnot
cycle. Removal of the membrane is an isothermal but irreversible process. This is
the same situation we encountered when molecules held on the left side a chamber
divided in half by a diaphragm were allowed to fill up the entire chamber by simply
removing the barrier very quickly. This is an adiabatic process since there is no
pressure involved in the expansion, and therefore no heat is required to carry this
irreversible process out. The entropy change for this process is:
S2(rxn) = R ln(V2/V1).
Remember we found this out using a reversible expansion, and invoking the heat
rule, S = dqrev/T. But the state function change is the same even when we get
from 1 to 2 irreversibly, as we are in this case. All we need is the initial and final
states to be the same P,T,V, and n values. Since no heat is exchanged with the
bath to carry out the V1 V2 expansion irreversibly in this way, the surroundings
are exactly the same before and after. Consequently,
S2(surr) = 0.
So overall for step 2:
S2(tot) = R ln (V2/V1)
which can be very large indeed if V2>>V1.
What is the physical situation in volume V2 after 1 mole HCN has been converted in
this fashion? The pressure of HCN is still very close to 1 atm because hardly any of
it was converted due to the large size of V2. But the partial pressure of the HNC is
quite small, and in fact calculable form the ideal gas law:
pHNC (final)= p1 atm (initial) x V1/V2.

[4]

So the overall change is that 1 mole of HCN at 1 atm is converted to HNC at very
small partial pressure pHNC. The volume ratio can be converted to the pressure ratio
using Eq. [4]:
S2(tot) = R ln {pHNC(initial (1 atm))/pHNC(final)} = R ln(p1/p2)
where the last line simplifies things by calling p 1 and p2 the initial and final
pressures of HNC.

For the overall process (step 1 + step 2), we can calculate the grand total entropy
change for converting 1 mole HCN at 1 atm to HNC at a partial pressure of p 2:
Stot = S1(tot) + S2(tot) = -D/T + R ln(p1/p2).
A little bit of reactant conversion to a small partial pressure of product can therefore
be hugely spontaneous (i.e., with a large entropy as p 1/p2 can be very large at the
beginning of a reaction (small p2), easily overcoming the cost, -D/T. It means you
cant stop a little bit of reaction from occurring at equilibrium even the reaction is
very endothermic. Equilibrium is achieved when Stot = 0, so we have:
R ln (p1/p2) = D/T
or
ln (p2/p1) = -D/RT

[5]

which is exactly what we got (see Eq. [1]) by applying the Gibbs free energy rule for
equilibrium constants. Putting P = pi/pref back in Eq. [5]:
PHNC = e-(D/RT)
The Boltzmann factor is seen to be a pure entropy thing.
MAJ/Nov 2010