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T dS Q 0. (4.1-1)
dU = Q P dV . (4.1-2)
T dS dU P dV 0. (4.1-3)
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
dUS,V 0. (4.1-6)
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)
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
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.
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.
d V dP
G= S dT . (4.3-1)
Therefore, variation of Gibbs energy with pressure and temperature is essential for
understanding phase stability.
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)
Gas Gas
Liquid Liquid
Solid Solid
vap
P Pm
Pressure Pressure
(a) (b)
~
Slope = S
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.
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
Temperature Tm Tb
Temperature
(a) (b)
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.
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.
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
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
dU = T dS P dV + mg dz (1)
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)
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
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.
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)
(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.
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
Z H
H IG /RT S
S IG /R
T ,P T ,P
Reference
Atake, T., I. Noriko, H. Kawaji, K. Matsuzaka and M. Akaogi, 2000, J. Chem. Thermodyn., 32,
217-227.