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The Thermodynamic Concept of Equilibrium
Intuitively, the concept of equilibrium conveys the message that something “balances out.”
Equilibrium describes a state of vanishing driving forces or gradients, where everything remains as
itis. if a system is in equilibrium, it retains its current state because there are no driving forces
causing anything to change.
If two materials have the same temperature, we say that they are in thermal equilibrium. No
exchange of heat takes places because there are no thermal gradients. For instance, a liquid and a
vapor phase are in thermal equilibrium when:
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(16.1)
We achieve mechanical equilibrium if two substances are found at the same pressure. No bulk
movement of fluids takes place because there are no pressure gradients. A liquid and a vapor
phase are in mechanical equilibrium when
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(16.2)
For a thermodynamic system to be in equilibrium, all intensive (temperature, pressure) and
extensive thermodynamic properties (U, G, A, H, S, etc) must be constants. Hence, the total change
in any of those properties (
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) must be zero at equilibrium.
Now we would like to have a concept of thermodynamic equilibrium for a vapor-liquid equilibrium.
Let us consider a closed, heterogeneous vapor-liquid system. Any changes in a total property of the
system will be the result of the changes of that property in the liquid phase plus the changes of that,
property in the vapor phase.
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(16.3)
In this case, liquid and vapor by themselves are not closed systems; they can exchange matter
between themselves but not with the surroundings, To elaborate more upon the concept of
equilibrium, let's look at equation (15.26c). Because it is written in terms of changes in pressure and
temperature, two measurable laboratory quantities, it is the “friendliest” of all fundamental
equations, We write it for both of the phases:This equation is not rendering properly due to an incompatible browser. See Technical
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(16.4a)
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(16.4b)
In (16.3), for
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, we get:
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(16.5)
Hence,
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(16.16)
Since at equilibrium all extensive properties, such as G, must remain constant, dG“! must be
zero. For this to hold true, and by inspection of equation (16.6), the conditions for thermodynamic
equilibrium are:
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(16.7)
E
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(16.8)
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(16.9)
It can be also proven that, at equilibrium, the total free energy of the system (G'°'@!)) must take a
minimum value; this reinforces the fact that dG''@=0 at equilibrium. The minimum Gibbs energy
criterion for equilibrium is a restatement of the second law of thermodynamics, from which we know
that the entropy of a system in equilibrium must be at its maximum, considering all of the possible
states for equilibrium.
It is somehow reasonable that for a true equilibrium condition there should be neither pressure nor
temperature gradients (equations 16.7 and 16.8). This is because equilibrium is, at the very least, a
state of lack of gradients. But what is equation (16.9) trying to tell us’? To demystify equation (16.9),
we recall that we are dealing with a closed system, hence, the total amount of moles per species:This equation is not rendering properly due to an incompatible browser. See Technical
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(16.10)
must be constant (we do not allow for chemical reactions within the system). Thus we write:
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(16.11)
Therefore,
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(16.12)
(16.12) into (16.11) yields:
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(16.13)
For equation (16.13) to hold true,
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(16.14)
We have then arrived at the criteria for vapor-liquid equilibria for a system at constant pressure and
temperature: the chemical potential of every species must be the same in both phases. We may
generalize this finding to any number of phases, for which the chemical potential of every species
must be the same in all phases. The chemical potential being the driving force which moves a
species from one phase to the other, equation (16.14) is physically reasonable. If the chemical
potential of a species in one phase is the same as that in the other, there is zero driving force and
thus a zero net transfer of species at equilibrium.
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