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Chapter 4

Equilibrium and Phase Stability


in One-Component Systems

The purpose of this chapter is to provide answers to the following questions:


(i) under what conditions are the two phases of a pure substance in equilibrium
with each other? and (ii) at a given temperature and pressure, in which form does
a pure substance existsolid, liquid, or gas?

4.1 Equilibrium Criteria for Closed Systems


For a closed system, the second law of thermodynamics, Eqn (1.6-8), states that

T dS Q  0. (4.1-1)

From the first law of thermodynamics

dU = Q P dV . (4.1-2)

Elimination of Q between Eqns (4.1-1) and (4.1-2) leads to

T dS dU P dV  0. (4.1-3)

4.1.1 Condition of Maximum Entropy


Under the conditions of constant internal energy and volume, Eqn (4.1-3) simplifies
to
dSU,V  0, (4.1-4)
where the subscripts U and V imply that these quantities are kept constant during
a process. Under these conditions, any spontaneous process tends to increase the
The Thermodynamics of Phase and Reaction Equilibria. DOI: http://dx.doi.org/B978-0-44-4594976.00004-9
2013 Elsevier B.V. All rights reserved. 105
106 Tosun

Constant U & V
Equilibrium

Entropy
dS = 0

Direction of a
spontaneous process

State of System

Figure 4.1: The equilibrium condition for constant internal energy and volume.

entropy of a system as shown in Fig. 4.1. When the system is at equilibrium, entropy
reaches its maximum value and this condition is mathematically expressed as

dSU,V = 0 At equilibrium. (4.1-5)

4.1.2 Condition of Minimum Internal Energy


When entropy and volume are kept constant, Eqn (4.1-3) simplifies to

dUS,V  0. (4.1-6)

Therefore, the internal energy of a system decreases as a result of a spontaneous


process under the conditions of constant entropy and volume. This phenomenon
can be explained as follows. Spontaneous processes lead to an increase in entropy.
In order to keep entropy constant, heat must be transferred to the surroundings
with a concomitant decrease in internal energy. When the system is at equilibrium,
internal energy reaches its minimum value and this condition is mathematically
expressed as
dUS,V = 0 At equilibrium. (4.1-7)

4.1.3 Condition of Minimum Helmholtz Energy


In differential form, Helmholtz energy is given by

dA = d(U TS) = dU S dT T dS. (4.1-8)

The use of Eqn (4.1-8) in Eqn (4.1-3) gives

dA + S dT + P dV  0. (4.1-9)
Equilibrium and Phase Stability in One-Component Systems 107

When temperature and volume are kept constant, Eqn (4.1-9) simplifies to

dAT ,V  0. (4.1-10)

Therefore, the Helmholtz energy of a system decreases as a result of a spontaneous


process under the conditions of constant temperature and volume. When the system
is at equilibrium, Helmholtz energy reaches its minimum value and this condition
is mathematically expressed as

dAT ,V = 0 At equilibrium. (4.1-11)

4.1.4 Condition of Minimum Gibbs Energy


In differential form, Gibbs energy is given by

dG = d(H TS) = d(U +PV TS) = dU +P dV +V dPT dS S dT . (4.1-12)

The use of Eqn (4.1-12) in Eqn (4.1-3) gives

dG + S dT V dP  0. (4.1-13)

When temperature and pressure are kept constant, Eqn (4.1-13) simplifies to

dGT ,P  0. (4.1-14)

Under these conditions, any spontaneous process tends to decrease the Gibbs energy
of a system as shown in Fig. 4.2. When the system is at equilibrium, Gibbs energy
reaches its minimum value and this condition is mathematically expressed as

dGT ,P = 0 At equilibrium. (4.1-15)

Since Gibbs energy describes equilibrium at conditions of constant temperature


and pressure, it is the most commonly used thermodynamic function in chemical
engineering applications.

4.2 Equilibrium Criteria for Open Systems


To develop the conditions for equilibrium, it is first necessary to develop the com-
bined first and second laws of thermodynamics for an open system. The first law
of thermodynamics for an open system, Eqn (1.5-3), is given by
in dnin H
H out dnout + Q + W = d(nU)
 sys (4.2-1)
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Constant T & P

Direction of a

Gibbs Energy
spontaneous process

dG = 0

Equilibrium

State of System

Figure 4.2: The equilibrium condition for constant temperature and pressure.

in which changes in kinetic and potential energies are considered negligible. On


the other hand, the entropy balance, Eqn (1.6-6), is written as
Q
Sgen = d(n
S)sys + 
Sout dnout 
Sin dnin . (4.2-2)
Tsys
To combine the first and the second law expressions, we have to restrict our
attention to processes that are reversible, i.e. Sgen = 0. Mass can be added and
withdrawn reversibly only if the properties of the entering and leaving mass are
identical to those of the system, i.e.
in = H
Tin = Tout = Tsys , Pin = Pout = Psys , H sys , 
out = H Sin = 
Sout = 
Ssys .
(4.2-3)
Under these conditions, Eqns (4.2-1) and (4.2-2) become
sys (dnin dnout) + Q + W = dUsys ,
H (4.2-4)
Q
0 = dSsys + Ssys (dnout dnin ) . (4.2-5)
Tsys
For a one-component system under consideration, the mass balance is expressed in
the form
dnin dnout = dnsys . (4.2-6)
Elimination of Q between Eqns (4.2-4) and (4.2-5) and the use of Eqn (4.2-6) lead
to
sys Tsys
dUsys = Tsys dSsys + W + (H Ssys )dnsys . (4.2-7)
If the only work is that of the expansion type of work, i.e. Psys dVsys , Eqn (4.2-7)
takes the form
dU = T dS P dV + (H  T S)dn, (4.2-8)
Equilibrium and Phase Stability in One-Component Systems 109

where the subscript sys is dropped with the understanding that all properties
belong to the system. The coefficient of dn is nothing more than the Gibbs energy
per mole, 
G, for a pure substance.1 Thus, Eqn (4.2-8) is expressed as
dU = T dS P dV + 
G dn. (4.2-9)
Consider an isolated system containing - and -phases of a pure substance.
Note that although the overall system is an isolated one, each phase may be consid-
ered an open system, i.e. there may be an exchange of mass and/or energy between
- and -phases. Since the system is isolated, then the total values of U, V , and n
are all constant, i.e.
U = U + U = constant dU = dU ,
V = V + V = constant dV = dV , (4.2-10)
n = n + n = constant dn = dn .
The equilibrium criterion for an isolated system is given by Eqn (4.1-5), i.e.
dS = dS + dS = 0. (4.2-11)
The total differential of entropy can be obtained from Eqn (4.2-9) as
1 P 
G
dS = dU + dV dn, (4.2-12)
T T T
so that
1 P 
G
dS = dU + dV dn , (4.2-13)
T T T
1 P 
G
dS = dU + dV dn . (4.2-14)
T T T
Substitution of Eqns (4.2-13) and (4.2-14) into Eqn (4.2-11) and making use of the
relationships given by Eqn (4.2-10) lead to
     
1 1 P P 
G 
G
dS = dU + dV dn = 0, (4.2-15)
T T T T T T
which can only be satisfied if the terms in parentheses in Eqn (4.2-15) are all equal
to zero. Therefore, the following conditions hold at equilibrium:
T = T Thermal equilibrium
P = P Mechanical equilibrium (4.2-16)
G = 
 G Chemical equilibrium.

1 Historically, for a single component system, Gibbs energy per mole has been called the chemical potential and
designated by , i.e. G = .
110 Tosun

Note that a temperature gradient implies the performance of a thermal work, i.e.
heat engine or heat pump, and a pressure gradient implies performance of mechan-
ical work, i.e. expansion/contraction work. The gradient of Gibbs energy, on the
other hand, implies performance of a chemical work.

4.3 Phase Stability


Why does water exist as a liquid when 0 < T < 100C under atmospheric condi-
tions at sea level? Why does CO2 exist as a gas under room conditions? To answer
such questions one should realize that any spontaneous process taking place at con-
stant temperature and pressure leads to a decrease in the Gibbs energy of a system.
The Gibbs energy reaches its minimum value when the system is at equilibrium.
In other words, at a given temperature and pressure, a pure substance is stable in a
phase in which it has the minimum Gibbs energy.2
In differential form, Gibbs energy of a pure substance is expressed as

d V dP 
G= S dT . (4.3-1)

Therefore, variation of Gibbs energy with pressure and temperature is essential for
understanding phase stability.

4.3.1 Change of Gibbs Energy with Pressure


Variation of Gibbs energy with pressure at constant temperature is
 

G
=
V. (4.3-2)
P
T

Since molar volume is always greater than zero, Eqn (4.3-2) implies that Gibbs
energy increases with increasing pressure under isothermal conditions.
For an ideal gas, integration of Eqn (4.3-2) at constant temperature gives
 P2  
IG RT P2
G = dP = RT ln . (4.3-3)
P1 P P1

2 Since G = H TS, the value of G is dependent on the terms H and TS. At high temperatures the term TS
dominates and, as a result, the phase with the highest value of entropy is the most stable. At low temperatures, the
term H dominates and the phase with the lowest value of enthalpy is the most stable.
Equilibrium and Phase Stability in One-Component Systems 111

Thus, Gibbs energy of an ideal gas increases exponentially with increasing pressure.
The molar volume of liquids and solids is almost independent of pressure. In
this case, integration of Eqn (4.3-2) at constant temperature leads to


GC = 
V C P, (4.3-4)

where the superscript C indicates the condensed phase, i.e. either liquid or solid.
Equation (4.3-4) indicates a linear variation of Gibbs energy with pressure, with a
slope being equal to 
V C.
If m is the slope of 
G versus P curve at any given temperature, then the above
discussion implies that
mV  mL > mS . (4.3-5)

While mL and mS are almost constant, mV changes exponentially with pressure.


Figure 4.3a indicates the variation of  G as a function of pressure for gas, liquid,
and solid phases.
As shown in Fig. 4.3b, when P < Pvap , the gas phase has the lowest Gibbs
energy and the substance exists as a gas since it is most stable in this phase. At
P = Pvap , molar Gibbs energies of the gas and liquid phases are equal to each other
or, in other words, the gas and liquid phases are in equilibrium. At this point the tem-
perature and pressure are called the saturation temperature (or boiling temperature)
and saturation pressure (or vapor pressure), respectively. When Pvap < P < Pm ,
the liquid phase has the minimum Gibbs energy and the substance exists as a liquid.
At P = Pm , molar Gibbs energies of the liquid and solid phases are equal to each

Gas Liquid Solid


Molar Gibbs Energy
Molar Gibbs Energy

Gas Gas

Liquid Liquid
Solid Solid

vap
P Pm
Pressure Pressure
(a) (b)

Figure 4.3: Variation of 


G as a function of P at constant T and stable equilibrium states.
112 Tosun

~
Slope = S

Molar Gibbs Energy


Temperature

Figure 4.4: Variation of 


G as a function of T at constant P.

other or, in other words, the liquid and solid phases are in equilibrium. At this point
the temperature and pressure are called the melting (or freezing) temperature and
melting pressure, respectively. When P > Pm , the solid phase is the most stable
phase since it has the lowest Gibbs energy.

4.3.2 Change of Gibbs Energy with Temperature


Variation of Gibbs energy with temperature at constant pressure is given by
 

G
=  S. (4.3-6)
T
P

Since the entropy is always positive, then the slope of 


G versus T is negative. More-
over, since 
S increases with temperature for all substances, then  G is a concave3
function of T as shown in Fig. 4.4.
Variation of Gibbs energies of different phases as a function of temperature
at constant pressure is shown in Fig. 4.5a. In plotting such a graph one should
remember that  SV >  SL > S S . As shown in Fig. 4.5b, solid, having the lowest
Gibbs energy, is the most stable phase when T < Tm . At T = Tm (melting or
freezing temperature), solid is in equilibrium with liquid and their molar Gibbs
energies are equal to each other. When Tm < T < Tb , the liquid phase is the stable
phase. At T = Tb (boiling or saturation temperature), the liquid and gas phases are
in equilibrium. The gas phase becomes the most stable phase for T > Tb .

3 A function f (x) is concave if the chord joining any two points lies entirely below the curve.
Equilibrium and Phase Stability in One-Component Systems 113

Solid Liquid Gas

Molar Gibbs Energy

Molar Gibbs Energy


Solid
Liquid Solid
Liquid
Gas
Gas

Temperature Tm Tb
Temperature
(a) (b)

Figure 4.5: Variation of 


G for different phases as a function of T at constant P and stable equilibrium
states.

Example 4.1 The following values are for saturated steam at 508.15 K. Show
that the liquid and vapor states of water are in equilibrium.

T (K) P vap (MPa)  L (kJ/kg)


H  V (kJ/kg)
H 
S L (kJ/kg K) 
S V (kJ/kg K)
508.15 3.06 1013.62 2804.2 2.6558 6.1791

Solution
When liquid and vapor phases of water are in equilibrium, then the number of
degrees of freedom is calculated from Eqn (1.1-4) as

F = C + 2 P = 1 + 2 2 = 1.

Therefore, either temperature or pressure has to be specified to fix the state of


the system. For saturated steam at 508.15 K, the corresponding vapor pressure
(or saturation pressure) is 3.06 MPa. Under the condition of equilibrium, Gibbs
energies of liquid and vapor must be equal to each other:
  L T
GL = H S L = 1013.62 (508.15)(2.6558) = 335.9248 kJ/kg,
  V T
GV = H S V = 2804.2 (508.15)(6.1791) = 335.7097 kJ/kg.
114 Tosun

Problems
Problem Related to Section 4.1
4.1 When the gravitational force is appreciable, Eqn (5) of Problem 2.11 indicates
that the change in Gibbs energy is expressed as
dG = V dP S dT + mg dz. (1)
(a) Since Gibbs energy reaches its minimum value under the condition of
equilibrium, i.e. dG = 0, conclude that
dT = 0 T is uniform (2)
and
dP
V dP + mg dz = 0 = g, (3)
dz
which is the hydrostatic pressure distribution. Keep in mind that the dis-
tance z is measured in the direction opposite to gravity.
(b) Since density, , is constant for liquids, show that the integration of
Eqn (3) gives
P = gz + C, (4)
where C is an integration constant.
(c) Density changes as a function of temperature and pressure in the case of
gases. Assuming ideal gas behavior, i.e.
PM
= , (5)
RT
show that the integration of Eqn (3) leads to
Mgz
ln P = + C, (6)
RT
where M is the molecular weight and C is an integration constant.
(d) Once the pressure in an oil reservoir decreases to low values, oil flow to
the well practically stops. Enhanced oil recovery (EOR) is a technique
used to recover oil that is left in the reservoir. One of the EOR techniques
is to inject high-pressure carbon dioxide into the reservoir. When CO2 is
mixed with oil, the resulting liquid has a lower viscosity, i.e. thinner, and
becomes less sticky. This process facilitates the flow of oil from the rock to
the well. Suppose that CO2 is injected into a well 4 km deep at a pressure
of 140 bar. If the temperature within the well is uniform at 310 K, estimate
the pressure at the bottom of the well.
(Answer: (d) 273.4 bar)
Equilibrium and Phase Stability in One-Component Systems 115

Problems Related to Section 4.2


4.2 Complete the following table without using the steam table:

T ( C)  L (kJ/kg)
H  V (kJ/kg)
H 
S L (kJ/kg K) 
S V (kJ/kg K)
567.69 2727.3 1.6870 6.9777
205 875.04 2.3780 6.3952
340 1594.2 2622.0 5.3357

Use T (K) = T ( C) + 273.15.


 V = 2795.9 kJ/kg, 
(Answer: T = 135 C, H S L = 3.6594 kJ/kg K).
4.3 When the gravitational force is appreciable, the combined first and second laws
of thermodynamics for a closed system lead to

dU = T dS P dV + mg dz (1)

as shown in Problem 2.11.


(a) In the case of an open system, show that the combined first and second
laws of thermodynamics give

dU = T dS P dV + mg dz + (
G + Mgz)dn, (2)

where m and M represent the mass and the molecular weight, respectively.
(b) Show that the change in Gibbs energy is given by

dG = V dP S dT + mg dz + (
G + Mgz)dn. (3)

(c) Under equilibrium conditions show that

dT = 0, (4)
V dP + mg dz = 0, (5)

G + Mgz = 0. (6)

(d) Differentiate Eqn (6) under constant temperature and conclude that
Eqns (5) and (6) both lead to hydrostatic pressure distribution as given by
Eqn (3) in Problem 4.1.
116 Tosun

Problems Related to Section 4.3


4.4 A function f (x) is convex if the chord joining any two points lies entirely
above the curve. Explain why Gibbs energy cannot be a convex function of
temperature at constant pressure. In other words, show that the following
plot of 
G versus T at constant pressure is impossible.

Temperature

4.5 An element X exists in nature in two different solid forms, X and X . The
standard Gibbs energy of formations of X and X at 298 K and atmospheric
pressure are 510 J/mol and 485 J/mol, respectively.

(a) Which form of X is the more stable at 298 K? Explain.


(b) The molar volumes of X and X are 25 cm3 /mol and 30 cm3 /mol, re-
spectively. Keeping the temperature constant at 298 K, does the increase
in pressure make X more stable than X ? If so, at what pressure will the
transition occur?
(c) The standard molar entropies of X and X are 23.6 J/mol K and
34.8 J/mol K, respectively. Under atmospheric pressure, does the increase
in temperature make X more stable than X ? If so, at what temperature
will the transition occur?

(Answer: (a) X , (b) 51 bar and (c) No)


4.6 Tin exists in two solid forms, white and gray tin. While white tin has a body-
centered tetragonal structure, the structure of gray tin is diamond cubic. The
enthalpy and entropy changes associated with the transformation of gray tin to
white tin at 298 K and atmospheric pressure are 2090 J/mol and 7.3 J/mol K,
respectively.
Equilibrium and Phase Stability in One-Component Systems 117

(a) Which form of tin is the more stable at 298 K?


(b) Under atmospheric pressure, estimate the temperature at which white and
gray tin coexist in equilibrium. Indicate your assumptions.

(Answer: (b) 286.3 K)

4.7 Phase transitions of SiO2 under high pressure are of interest to earth scientists.
Atake et al. (2000) reported that the enthalpy and entropy changes during -
quartz to coesite (polymorph of quartz) transition at 298 K and atmospheric
pressure are 3400 J/mol and 2.16 J/mol K, respectively. The molar volume
of -quartz is 22.688 106 m3 /mol and the molar volume of coesite is
20.6 106 m3 /mol. At 298 K, what is the pressure at which these two forms
of SiO2 will be in equilibrium?
(Answer: 1.94 GPa)

4.8 The vapor pressure of water as a function of temperature is given by

vap 6.6075 103 10.1855 105 17.7039 107


ln PH2 O = 13.8365 + ,
T T2 T3
300  T  600,
vap
where PH2 O is in bar and T is in K.

(a) Estimate the minimum pressure at which water exists as a liquid at 350 K.
(b) Estimate the maximum pressure at which water exists as a vapor at 500 K.

(Answer: (a) 0.425 bar and (b) 26.56 bar)

4.9 A pure substance X flows through a heat exchanger under steady conditions as
shown in the figure below. The inlet and outlet streams are single-phase and
the ideal gas heat capacity is 
CP = 11.5R.

T = 350 K T = 250 K
P = 8 bar P = 1 bar
118 Tosun

Estimate the amount of heat added to or removed from substance X using


the following information provided from the solutions of the Peng-Robinson
equation of state at the inlet and outlet conditions:

Z H
H  IG /RT S 
S IG /R
T ,P T ,P

0.0334 5.868 6.088


Inlet 0.0895 3.107 3.465
0.8573 0.410 0.275
0.0043 10.451 9.988
Outlet 0.0334 2.673 4.033
0.9588 0.106 0.066

(Answer: 30,090 J/mol)

Reference
Atake, T., I. Noriko, H. Kawaji, K. Matsuzaka and M. Akaogi, 2000, J. Chem. Thermodyn., 32,
217-227.