phase-and-chemical-equilibrium-conditions-derivation.doc v.

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Phase and Chemical Equilibrium
Gibbs relation for open systems using Chemical Potential (refer to Sonntag (SBVW) Section 13.10)
Internal energy: dU = TdS - PdV + i dniI SBVW Eq. (13.71)
Definitions of other thermodynamic potentials: Enthalpy: H U + PV;
Helmholtz Free Energy: A U - TS (SBVW Eq. 13.12) (note: this A has nothing to do with "Availability");
Gibbs Free Energy: G H - TS (SBVW Eq. 13.14).
Taking the total differential of these defining equations and substituting (13.71) for dU yields
additional "TdS equations",
dH = TdS + VdP + i dni
dA = -SdT -PdV + i dni
dG = -SdT + VdP + i dni SBVW Eq. (13.73)
All the potentials are now functions of the number of moles of each species in the system, as well as two other
variables such as (S,P), (T,P), or whatever. All partial derivatives must specify which of this multitude
of variables is being held constant. So, for example,
G (T , P, all n ' s )
V =
P
T ,all n j

G (T , P, all n ' s )
i =
ni n ji

Requirements for Equilibrium

What conditions are required for equilibrium in multicomponent, multiphase systems?
Examples:
a. Ice + water
b. Humid air over a lake
c. Carbon dioxide in the atmosphere and in the ocean
d. Salt water + "wet" salt crystals.
e. Gasoline + alcohol.

Starting axiom: An isolated system is in equilibrium when no spontaneous process can occur.

Here is an outline of the train of thought followed in the rest of this document:
(1) For an isolated system, S increases during any spontaneous process and therefore S is at its maximum
possible value in equilibrium;
(2) As a consequence, T must be spatially uniform in equilibrium.
(3) For a system at constant volume in thermal equilibrium with a temperature reservoir at T=TR, during any
spontaneous process dA 0 and therefore A is at its minimum possible value in equilibrium.
(4) As a consequence, P must be spatially uniform in equilibrium.
(5) For a system at constant pressure in thermal and mechanical equilibrium with a reservoir at T = TR and
P = PR, during any spontaneous process dG 0, and therefore G is at its minimum possible value in
equilibrium.
(6) As a consequence, the chemical potential of a species is spatially uniform in equilibrium.

We will then be able to conclude that the unifying statement about situations a-e above is that in equilibrium T,
P, and the chemical potentials of each species are spatially uniform. More specifically, whenever two systems
can exchange heat, equilibrium requires their temperatures to be the same; whenever two systems can
exchange volume (i.e. do PV work on each other), equilibrium requires that their pressures be the same;
whenever two systems can exchange chemical species, equilibrium requires that the chemical potential of each
species be spatially uniform, spanning both systems.
phase-and-chemical-equilibrium-conditions-derivation.doc v.3 page 2

Start with: An isolated system is in equilibrium when no spontaneous process can occur.
Q
(1) 2nd law For any process, dS . (This is Eq. (0.2) of handout, "Entropy Change Examples")
TRes
Q
For any real process, dS > and only in the limit of infinitely slow ideal processes where all temperature
TRes
differences vanish and all friction vanishes and all forces balance, does the equality hold.
For a completely isolated system, Q = 0 and W = 0
dS 0 for any process in a completely isolated system.
The only possible process in a completely isolated system is a spontaneous process.
Hence, for a spontaneous process occurring within a completely isolated system dS > 0.
For an isolated system in equilibrium, therefore, the statement "no spontaneous process can occur" means
that S is at its maximum possible value, such that a decrease in the system's entropy would result from
all possible variations S (it is customary to use S to denote hypothetical variations and dS for actual
changes) in the state of the system (or all possible variations in the S
states of its subsystems, e.g resulting from a transfer of Q between eqm
two parts of the system, as illustrated in (2) below).
dS > 0 (spontaneous process, isolated (i.e. const. E,V) control mass)

t.

sp
on
(S)E ,V

on
0 (virtual variation of isolated control mass away from equilibrium)

sp

t.
T1=T2 Q12
(2) Let's remind ourselves of what this means for the case of a system composed of two subsystems at
temperatures T1 and T2<T1 that can exchange heat but not work. Let each subsystem be internally
equilibrated, so that the entire temperature discontinuity occurs over the wall separating them.
Subsyst em 1 Subsyst em 2 rigid adiabat ic wall
U1 ,S1 U2 ,S2
rigid diat hermal wall
T1 T2 <T1

If T1>T2 can the system be in equilibrium?

To find out, transfer a small amount of heat Q both "uphill" from 2 to 1 and "downhill" from 1 to 2 and in each
case evaluate STOT = S1+ S2. If the result in either case is positive, then we can't have been in
equilibrium because the result would conflict with the second boxed equation above. It turns out that
only the "downhill" transfer tells us something important in this case, so let's work that out. Transfer the
heat so slowly that each system remains internally in equilibrium at all times. This means that the heat
transfer process for each system is internally reversible but externally irreversible; the only
irreversibility is heat transfer through the wall.
For an internally reversible process the change in S equals the heat absorbed by the system divided by the
temperature of the system just inside the control surface for that system.
The process is internally reversible for each of the two subsystems.
S2 = +Q / T2
S1 = -Q / T1
___________
1 1
STOT = Q > 0 because T1>T2.
T2 T1
We have found a process that can occur within this isolated system (i.e., a virtual variation from the starting
configuration by a small amount of heat transfer) that increases STOT. This violates the stated condition
for equilibrium. Therefore the system cannot be in equilibrium.
phase-and-chemical-equilibrium-conditions-derivation.doc v.3 page 3

Likewise, if the temperature difference were the opposite way, we would find that transferring heat "downhill"
from 2 to 1 increased STOT, violating the conditions for equilibrium. (In either case, if we were to
analyze the transfer of heat "uphill" we would find a decrease in STOT, which wouldn't prove anything.)

Therefore we are forced to conclude that the temperature must be uniform throughout a system as a requirement
for equilibrium.
Notes:
1. When T1 = T2 there is one permitted infinitesimally slow ideal process: the transfer of an infinitesimal
amount of heat at constant T. However, when each side has a single phase, transferring a finite amount
of heat between finite systems will create a finite temperature difference and the latter part of the
transfer will violate the second law.
2. In the above derivation, no work and no heat are exchanged with the environment.
3. If we restrict our discussion to a simple compressible substance (which we will do from here on), this
means that E and V are constant.

In equilibrium, all possible variations in S while holding E and V constant satisfy (S)E,V 0

(3) When the system is not isolated, consider the system + surroundings ("reservoir") as isolated at T = TR.
What are the conditions for a spontaneous process to occur in the system?
Here we show that:
For a system at constant volume in thermal equilibrium with a temperature reservoir at T=TR, during any
spontaneous process dA 0 and therefore AU-TS is at its minimum possible value in equilibrium. (On
your homework you will show that dG 0 for a spontaneous process in a system at constant T and P).
Consider a system with rigid diathermal walls (constant V), inside which an internally irreversible
process (e.g., chemical reactions, phase change, etc.) is occurring. However, all processes occurring
within the reservoir, as well as the heat exchange between the reservoir and the system, are reversible.
We reversibly transfer an infinitesimal bit of heat Q to the system from the reservoir (this is
permissible because they're at the same temperature) while the aforementioned spontaneous, irreversible
process is going on in the system.

Re se r v o ir
UR,SR,T R,PR,V R rigid adiabat ic wall

Sy st em
Q
U, S, T , P, V

rigid diat hermal wall

Because the system is in thermal equilibrium with the reservoir (T=TR) and the heat transfer is reversible,
Q Q
the entropy change of the reservoir can be written dSR = =
T TR
Because there is an internally irreversible process occurring in the system, dS + dSR 0, or dS - dSR.
phase-and-chemical-equilibrium-conditions-derivation.doc v.3 page 4
Q
Plugging in +Q/T for -dSR in this last equation yields dS .
T
Now we examine what this implies for changes in U and A. Because there is no PV work exchanged
(system at constant volume) and no other form of work is permitted (simple compressible substance),
dU = Q from the First Law. But we just showed that Q TdS. Hence,
dU TdS.
dU - TdS 0.
d(U - TS) 0 because we're at constant T = TR and so dT = 0 and it can be taken inside the differential.
dA 0 by the definition of Helmholtz Free Energy A U - TS.

Systems held at constant T and V spontaneously evolve to the lowest possible Helmholtz Free Energy,
A=U-TS. Closed systems (constant mass or number of moles) evolve to minimize their value of a=u-Ts.

Why to crystals melt at high T? Liquid has higher s, higher u than crystal.
At high enough T, the -Ts term dominates over the u term and the stable (i.e., lowest a) phase is the one with the
highest s.
At low enough T, the u term dominates over the -Ts term the stable (i.e., lowest a) phase is the one with the
lowest u.
The transition (two-phase solid-liquid equilibrium at constant volume) occurs when uliq-Tsliq=usol-Tsso, this
temperature is known as the equilibrium melting point at constant volume. We shall see how this gets modified
(G replaces A) if the process is carried out at constant pressure as is typical in practice.

So, we have shown that for a spontaneous process occurring within a system at constant volume and in thermal
equilibrium with a reservoir at temperature T, the Helmholtz free energy A must decrease. Therefore,
when the system is in equilibrium and no more spontaneous processes can occur, A must be at its
minimum possible value:
In equilibrium, all possible variations in A while holding T and V constant satisfy (A)T,V 0.

dA < 0 (spontaneous process, system at constant T,V)

( A)T ,V 0 (virtual variation of constant T,V system away from equilibrium)
A
sp

t.
on
on

sp
.t

eqm
Q12 or V2

(4) Now we show that the previous derivation implies that P must be spatially uniform in equilibrium.
Consider a system composed of two subsystems with pressures P1 and P2 as shown below; both
subsystems are in thermal equilibrium with the reservoir and they can do PV work on each other but no
work can be done on the reservoir: T1 = T2 = TR; V1 + V2 = constant dV2 = -dV1.
phase-and-chemical-equilibrium-conditions-derivation.doc v.3 page 5

rigid diat hermal wall

Re se r v o ir
UR,SR,T R,PR,V R

Subsyst em 1 Subsyst em 2
U1 ,S1 ,P1 ,V 1 U2 ,S2 ,P2 ,V 2
T=T R T=T R

movable diat hermal wall

Suppose now that P1 > P2. Can the system be in equilibrium? To find out, let's examine the variation in
Helmholtz free energy A when V1 is increased and V2 is decreased by an amount V1 > 0 slowly
enough that temperature uniformity is maintained. From the equation on the first page for dA,

A1 = -S1 dT - P1 dV1 = - P1 V1 because T is constant so dT is zero.

A2 = -S2 dT - P2 dV2 = + P2 V1. Summing them,
Asystem = (P2 - P1) V1 which is < 0 because we already specified that P1 > P2 and V1 > 0.

We have found a process that can occur within this constant-volume, constant-temperature system that
decreases its Helmholtz free energy. This violates the condition we just derived for equilibrium.
Therefore the system cannot be in equilibrium.
If we had moved the wall the other way, V1 < 0, we would have found that A increases. This would not
have violated the condition for equilibrium, but we need only find a single violating process in order to
conclude that the system is not in equilibrium. If the pressure difference were the opposite way, we
would find that moving the wall one way (toward the lower-pressure subsystem) violates the condition
for equilibrium.
Therefore we are forced to conclude that the pressure must be uniform throughout a system for equilibrium.

(5) You can prove that for a system at constant pressure in thermal and mechanical equilibrium with a reservoir
at T = TR and P = PR, during any spontaneous process dG 0, and therefore G is at its minimum
possible value in equilibrium: (G)T,P 0. The proof is entirely analogous to that for A.
dG < 0 (spontaneous process, system at constant T,P)
(G )T , P 0 (virtual variation of constant T,P system away from equilibrium)
One can also use similar arguments to show that (U)S,V 0 and (H)S,P 0.

(6) Now we show that the condition (G)T,P 0 for any virtual variation away from equilibrium implies that
the chemical potential, , must be spatially uniform in equilibrium. Consider a system composed of two
subsystems with a single component with chemical potentials 1 and 2 as shown below; both
subsystems are in thermal and mechanical equilibrium with the reservoir and they transfer mass between
each other but no mass can be transferred to or from the reservoir:
T1 = T2 = TR; P1 = P2 = PR; n1 + n2 = constant dn2 = - dn1.
phase-and-chemical-equilibrium-conditions-derivation.doc v.3 page 6

movable diat hermal wall

Re se r v o ir
UR,SR,T R,PR,V R

Subsyst em 1 Subsyst em 2
U1 ,S1 , 1 ,n 1 U2 ,S2 , 2 ,n 2
T= T R,P= PR T= T R,P= PR

rigid porous wall

Suppose now that 1 > 2 and let's examine the variation in Gibbs free energy G when we (slowly enough
for thermal and mechanical equilibrium to be maintained) transfer n2 > 0 moles from subsystem 1 to
subsystem 2: dn2 = - dn1 = n2. From the equation for dG on the first page,
G1 = - S1 dT + V1 dP + 1 dn1 = - 1 n2 because the system is at constant T and P so dT = 0, dP = 0.
G2 = - S2 dT + V2 dP + 2 dn2 = 2 n2 and, adding them,
Gsystem = (2 - 1) n2 which is < 0 because we already specified that 1 > 2 and n2 > 0.
We have found a process that can occur within this constant-pressure, constant-temperature system that
decreases its Gibbs free energy. This violates the condition for equilibrium that you will prove in your
homework. Therefore the system cannot be in equilibrium. We are forced to conclude that equilibrium
requires the chemical potential to be uniform throughout a system.
If you repeat this exercise for a system at constant volume, letting the two subsystems exchange matter, you
can show that the requirement (A)T,V 0 forces you to conclude that the chemical potential must be
uniform throughout the system for equilibrium. So you get the same conclusion whether you're at
constant P or constant V.

A consideration of all possible sets of circumstances shows that

Whenever two (sub)systems can exchange heat, equilibrium requires their temperatures to be the same;
Whenever two (sub)systems can exchange volume (i.e. do PV work on each other), equilibrium requires that
their pressures be the same;
Whenever two (sub)systems can exchange a particular chemical species, equilibrium requires that the chemical
potential of that particular species be the same in each system.

Notes:
1. The chemical potential of any particular species has to be the same everywhere, but the chemical potentials
of different species have to be equal to each other only if they can interconvert, e.g. "boat" vs. "chair"
configuration of cyclohexane. If other reactions are permitted then there is a relationship between the
chemical potentials of the various species in equilibrium that you can determine by minimizing the
appropriate free energy with respect to the extent of the reaction.

2. You can think of T as the "thermal potential", P as the "mechanical potential", and as the "chemical
potential": In all cases, stuff goes spontaneously from high to low potential, and equilibrium is reached
eventually when the potential becomes the same everywhere. Note that the potential is an intensive
property, it doesn't change when you double the size of the system by putting two identical systems next
to each other and drawing a box around them.