c 2011 Ismail Tosun

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?, (ii) at a given temperature and pressure, in which form does a pure substance exist - solid, liquid, or gas? 4.1 EQUILIBRIUM CRITERIA FOR CLOSED SYSTEMS For a closed system, the second law of thermodynamics, Eq. (1.6-8), states that T dS Q 0 From the rst law of thermodynamics dU = Q P dV Elimination of Q between Eqs. (4.1-1) and (4.1-2) leads to T dS dU P dV 0 4.1.1 Condition of Maximum Entropy Under the conditions of constant internal energy and volume, Eq. (4.1-3) simplies to dSU,V 0 (4.1-4) (4.1-3) (4.1-2) (4.1-1)

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 entropy of a system as shown in Figure 4.1. When the system is at equilibrium, entropy reaches its maximum value and this condition is mathematically expressed as dSU,V = 0
Equilibrium

At equilibrium

(4.1-5)

Entropy

dS = 0

Direction of a spontaneous process Constant U & V

State of System

Figure 4.1

The equilibrium condition for constant internal energy and volume. 83

4.1.2 Condition of Minimum Internal Energy When entropy and volume are kept constant, Eq. (4.1-3) simplies 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 dierential form, Helmholtz energy is given by dA = d(U T S ) = dU S dT T dS The use of Eq. (4.1-8) in Eq. (4.1-3) gives dA + S dT + P dV 0 When temperature and volume are kept constant, Eq. (4.1-9) simplies to dAT,V 0 (4.1-10) (4.1-9) (4.1-8)

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 dierential form, Gibbs energy is given by dG = d(H T S ) = d(U + P V T S ) The use of Eq. (4.1-12) in Eq. (4.1-3) gives dG + S dT V dP 0 When temperature and pressure are kept constant, Eq. (4.1-13) simplies to dGT,P 0 (4.1-14) (4.1-13) = dU + P dV + V dP T dS S dT (4.1-12)

Under these conditions, any spontaneous process tends to decrease the Gibbs energy of a system as shown in Figure 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)

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Direction of a spontaneous process Gibbs Energy

dG = 0 Constant P & T Equilibrium State of System

Figure 4.2

The equilibrium condition for constant temperature and pressure.

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 rst necessary to develop the combined rst and second laws of thermodynamics for an open system. The rst law of thermodynamics for an open system, Eq. (1.5-3), is given by e in dnin H e out dnout + Q + W = d(nU e )sys H (4.2-1)

in which changes in kinetic and potential energies are considered negligible. On the other hand, the entropy balance, Eq. (1.6-6), is written as e)sys + S eout dnout S ein dnin Q Sgen = d(nS Tsys (4.2-2)

To combine the rst 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., Tin = Tout = Tsys Pin = Pout = Psys e out = H e sys e in = H H eout = S esys ein = S S (4.2-3) (4.2-4) (4.2-5)

Under these conditions, Eqs. (4.2-1) and (4.2-2) become

e sys (dnin dnout ) + Q + W = dUsys H esys (dnout dnin ) Q 0 = dSsys + S Tsys dnin dnout = dnsys Elimination of Q between Eqs. (4.2-4) and (4.2-5) and the use of Eq. (4.2-6) lead to e sys Tsys S esys ) dnsys dUsys = Tsys dSsys + W + (H 85

For a one-component system under consideration, the mass balance is expressed in the form (4.2-6)

(4.2-7)

where the subscript "sys " is dropped with the understanding that all properties belong to the e, for a pure system. The coecient of dn is nothing more than the Gibbs energy per mole, G 1 substance . Thus, Eq. (4.2-8) is expressed as 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 considered 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 V = V + V = constant n = n + n = constant dU = dU dV = dV dn = dn (4.2-11) (4.2-10) e dn dU = T dS P dV + G (4.2-9)

If the only work is that of the expansion type of work, i.e., Psys dVsys , Eq. (4.2-7) takes the form e TS e) dn dU = T dS P dV + (H (4.2-8)

The equilibrium criterion for an isolated system is given by Eq. (4.1-4), i.e., dS = dS + dS = 0 The total dierential of entropy can be obtained from Eq. (4.2-9) as dS = so that e P G 1 dU + dV dn T T T (4.2-12)

which can only be satised if the terms in parentheses in Eq. (4.2-15) are all equal to zero. Therefore, the following conditions hold at equilibrium: T = T P = P e = G e G Thermal equilibrium Mechanical equilibrium Chemical equilibrium

e 1 P G dU + dV dn (4.2-13) T T T e P G 1 dU + dV dn (4.2-14) dS = T T T Substitution of Eqs. (4.2-13) and (4.2-14) into Eq. (4.2-11) and making use of the relationships given by Eq. (4.2-10) lead to ! e e G P P 1 1 G (4.2-15) dS = dU + dV dn = 0 T T T T T T dS =

(4.2-16)

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 mechanical work, i.e., expansion/contraction work. The gradient of Gibbs energy, on the other hand, implies performance of a chemical work.
Historically, for a single component system, Gibbs energy per mole has been called the chemical potential e = . and designated by , i.e., G
1

86

4.3 PHASE STABILITY Why does water exist as a liquid when 0 < T < 100 C under atmospheric conditions 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 constant 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 energy2 . In dierential form, Gibbs energy of a pure substance is expressed as e=V e dP S e dT dG (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 ! e G e =V P
T

(4.3-2)

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 Eq. (4.3-2) at constant temperature leads to e C P eC = V G (4.3-4)

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

While mL and mS are almost constant, mV changes exponentially with pressure. Figure 4.3-a e as a function of pressure for gas, liquid, and solid phases. indicates the variation of G As shown in Figure 4.3-b, when P < P vap , 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 = P vap , 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 temperature and pressure are called the saturation temperature (or boiling temperature) and saturation pressure (or vapor
Since G = H T S , the value of G is dependent on the terms "H " and "T S ". At high temperatures the term "T S " 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.
2

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 e C. V e versus P curve at any given temperature, then the above discussion If m is the slope of G implies that (4.3-5) mV mL > mS

87

~ G

~ G

Gas

Liquid

Solid

Gas Liquid

Gas Liquid

Solid

Solid

P (a)

P vap (b)

Pm

Figure 4.3

pressure), respectively. When P vap < 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 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 ! e G e = S T
P

e as a function of P at constant T and stable equilibrium states. Variation of G

(4.3-6)

e versus T is negative. Moreover, since Since the entropy is always positive, then the slope of G e e S increases with temperature for all substances, then G is a concave3 function of T as shown in Figure 4.4.

Gibbs Energy

~ G

~ slope = S

T
Temperatur e

A function f (x) is concave if the chord joining any two points lies entirely below the curve.

e as a function of T at constant P . Figure 4.4 Variation of G 88

Variation of Gibbs energies of dierent phases as a function of temperature at constant eV > pressure is shown in Figure 4.5-a. In plotting such a graph one should remember that S eS . As shown in Figure 4.5-b, solid, having the lowest Gibbs energy, is the most stable eL > S S 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 .
Solid ~ G Gas Liquid Gas Liquid ~ G Liquid Gas

Solid

Solid

T (a)

Tm (b)

Tb

e for dierent phases as a function of T at constant P and stable Figure 4.5 Variation of G 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) 508.15 Solution When liquid and vapor phases of water are in equilibrium, then the number of degrees of freedom is calculated from Eq. (1.1-4) as F =C +2P =1+22=1 Therefore, either temperature or pressure has to be specied to x 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 : bL TS bL = 1013.62 (508.15)(2.6558) = 335.9248 kJ/ kg bL = H G bV TS bV = 2804.2 (508.15)(6.1791) = 335.7097 kJ/ kg bV = H G P vap ( MPa) 3.06 b L ( kJ/ kg) H 1013.62 b V ( kJ/ kg) H 2804.2 bL ( kJ/ kg. K) S 2.6558 bV ( kJ/ kg. K) S 6.1791

REFERENCE Atake, T., I. Noriko, H. Kawaji, K. Matsuzaka and M. Akaogi, 2000, J. Chem. Thermodynamics, 32, 217-227. 89

PROBLEMS Problem related to Section 4.1 4.1 When the gravitational force is appreciable, Eq. (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 and V dP + mg dz = 0 T is uniform (2)

dP (3) = g dz which is the hydrostatic pressure distribution. Keep in mind that the distance z is measured in the direction opposite to gravity. b) Since density, , is constant for liquids, show that the integration of Eq. (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 Eq. (3) leads to M gz +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 ow 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 ow 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) ln P = Problems related to Section 4.2 4.2 Complete the following table without using the steam table: T ( C) 205 340 b L ( kJ/ kg) H 567.69 875.04 1594.2 b V ( kJ/ kg) H 2727.3 2622.0 bL ( kJ/ kg. K) S 1.6870 2.3780 bV ( kJ/ kg. K) S 6.9777 6.3952 5.3357

Use T ( K) = T ( C) + 273.15. b V = 2795.3 kJ/ kg, S bL = 3.6590 kJ/ kg. K) (Answer: T = 135 C, H 90

4.3 When the gravitational force is appreciable, the combined rst and second laws of thermodynamics for a closed system lead to dU = T dS P dV + mg dz as shown in Problem 2.11. a) In the case of an open system, show that the combined rst and second laws of thermodynamics give e + M gz ) dn dU = T dS P dV + mg dz + (G (2) e + M gz ) dn dG = V dP S dT + mg dz + (G dT = 0 V dP + mg dz = 0 e + M gz = 0 G (3) (1)

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

c) Under equilibrium conditions show that

(4) (5) (6)

d) Dierentiate Eq. (6) under constant temperature and conclude that Eqs. (5) and (6) both lead to hydrostatic pressure distribution as given by Eq. (3) in Problem 4.1. 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. e vs T at constant pressure is impossible. In other words, show that the following plot of G
~ G

4.5 An element X exists in nature in two dierent 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, respectively. 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 c) No) 91

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. 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 G Pa) 4.8 The vapor pressure of water as a function of temperature is given by
vap = 13.8365 ln PH 2O

6.6075 103 10.1855 105 17.7039 107 + T T2 T3

300 T 600

vap where PH is in bar and T is in K. 2O

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 b) 26.56 bar) 4.9 A pure substance X ows through a heat exchanger under steady conditions as shown in the gure below. The inlet and outlet streams are single-phase and the ideal gas heat capacity e = 11.5 R. is C P
T = 350 K P = 8 bar T = 250 K P = 1 bar

Q=?

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 0.0334 0.0895 0.8573 0.0043 0.0334 0.9588 e H e IG H /RT eS eIG S /R

T,P

T,P

Inlet

Outlet

10.451 2.673 0.106

5.868 3.107 0.410

9.988 4.033 0.066

6.088 3.465 0.275

(Answer: 30, 090 J/ mol) 92