c 2011 Ismail Tosun

Chapter 5 Fugacity of a Pure Component

This chapter introduces a new concept called fugacity, which is the basis for establishing equilibrium criteria between dierent phases of a pure substance. After showing how to calculate this quantity for gases, liquids, and solids, the variation of temperature with pressure (or vice versa) during phase transformation of pure substances will be discussed. 5.1 MOLAR GIBBS ENERGY OF A PURE IDEAL GAS For a pure substance, molar Gibbs energy is given in dierential form as e e e dG = V dP S dT RT e V IG = P (5.1-1)

The ideal gas equation of state relates the molar volume to pressure as (5.1-2)

Substitution of Eq. (5.1-2) into Eq. (5.1-1) leads to e dGIG =

At constant temperature, Eq. (5.1-3) reduces to e dGIG = RT d ln P P Po

RT e e dP S dT = RT d ln P S dT P at constant T

(5.1-3)

(5.1-4)

Integration of Eq. (5.1-4) at constant temperature from the standard state pressure, P o , to the state of interest at which the pressure is P gives ln = e e GIG (T, P ) GIG (T, P o ) RT (5.1-5)

5.2 DEFINITION OF FUGACITY AND FUGACITY COEFFICIENT Equation (5.1-5) is valid only for pure, ideal gases. In order to generalize it, in 1901 Gilbert Newton Lewis1 introduced a function fi , called the fugacity of pure component i, in terms of the departure function for molar Gibbs energy as ln e e (Gi GIG )T,P fi (T, P ) i = P RT e e eIG e (Si Si )T,P (Hi HiIG )T,P = RT R

(5.2-1)

Professor of physical chemistry and the dean of the College of Chemistry at University of California, Berkeley.

93

subject to the following constraint fi /P 1 as P 0 (ideal gas state) (5.2-2)

which applies to solid, liquid, and gas. The fugacity coecient of pure component i, i , is dened as the ratio of the fugacity to the pressure, i.e., fi (5.2-3) i = P It is a measure of the deviation of the system from ideal gas behavior, i.e., i = 1 for an ideal gas. Note that both fugacity and the fugacity coecient are intensive properties of the system and are a function of any two other intensive properties, such as temperature and pressure, for a single-phase pure material. Fugacity coecient may be greater or less than unity as shown in Figure 5.1.
i 1

Figure 5.1

Variation of the fugacity coecient with pressure.

Addition of Eqs. (5.1-5) and (5.2-1) leads to an alternative expression for the fugacity of pure component i in the form e ei Gi (T, P ) = GIG (T, P o ) RT ln P o + RT ln fi (T, P ) e Gi (T, P ) = i (T ) + RT ln fi (T, P ) ei i (T ) = GIG (T, P o ) RT ln P o at constant T (5.2-4)

or

(5.2-5)

where i (T ) is the molar Gibbs energy of pure component i at unit fugacity, and is dened by (5.2-6)

Dierentiation of Eq. (5.2-5) at constant temperature gives e dGi = RT d ln fi

(5.2-7)

When two phases of a pure substance are in equilibrium, we have T = T P = P e ei G = G i (5.2-8)

Letting T = T = T and P = P = P , equality of molar Gibbs energies leads to i (T ) + RT ln fi (T, P ) = i (T ) + RT ln fi (T, P ) fi (T, P ) = fi (T, P ) (5.2-9)

indicating that fugacities of a pure component must be equal to each other under the conditions of equilibrium. 94

The word fugacity comes from the same root as "fugitive". It can be thought of as a degree of "discomfort". The higher the fugacity, the more uncomfortable a molecule is in a given phase. To ease the measure of discomfort, a molecule escapes to another phase in which its fugacity is lower. For this reason, fugacity is also called "escaping tendency", the measure of which is molar Gibbs energy. All spontaneous physical and/or chemical processes take place in the direction of decreasing fugacity and molar Gibbs energy. For example, the driving force for mass transfer is the dierence in fugacity. At constant temperature, Eq. (5.1-1) reduces to e e dGi = Vi dP (5.2-10)

Substitution of Eq. (5.2-10) into Eq. (5.2-7) gives

Subtraction of the term RT d ln P from both sides of Eq. (5.2-11) and integration from an ideal gas state to any state lead to ! Z P e Vi 1 fi = ln i = ln T = constant (5.2-12) dP P RT P 0 which is applicable to gases, liquids, and solids. Fugacity (or fugacity coecient) can be calculated from either Eq. (5.2-1) or Eq. (5.2-12). 5.3 FUGACITY OF A PURE GASEOUS SPECIES Fugacity of a pure gas at a given temperature and pressure can be calculated from Eq. (5.2-12), i.e., ! Z P e Vi 1 ln V = T = constant (5.3-1) dP i RT P 0 or ln V = i Z
P 0

e RT d ln fi = Vi dP

(5.2-11)

ZiV 1 P

dP

T = constant

(5.3-2)

At low pressures, gases behave ideally, i.e., ZiV = 1, and Eq. (5.3-2) leads to ln V = 0 i V = 1 or fiV (T, P ) = P i (5.3-3)

indicating that for a pure gas at low pressures the fugacity coecient is unity and the fugacity is equal to the total pressure. 5.3.1 Fugacity from Volume-Explicit Equations of State e e Substitution of Vi = Vi (P, T ) into Eq. (5.3-1) and integration of the resulting equation either analytically or numerically give the fugacity of a gas at a specied temperature and pressure. Example 5.1 Calculate the fugacity coecient of ammonia at 350 K and 50 bar if the equation of state is given as e P (V b) = RT 95

where b = 37.3 cm3 / mol.

Solution From the given equation of state RT e VNH 3 = b + P Substitution of Eq. (1) into Eq. (5.3-1) gives Z 50 b 1 1 bP 50 ln NH 3 = + dP = RT P P RT 0 0 (37.3)(50) = 0.064 = (83.14)(350) Therefore, NH3 = 1.066 (1)

5.3.2 Fugacity from Property Tables If property tables are available, then fugacity can be calculated directly without using an equation of state as shown in the following example. Example 5.2 Calculate the fugacity of steam at 873 K and 50 bar using the following data: T ( K) 873 873 Solution Let the values of temperature and pressure at states 1 and 2 be (873 K, 0.1 bar) and (873 K, 50 bar), respectively. From Eq. (5.2-5) e G1 = (873 K) + RT ln f1 Subtraction of Eq. (1) from Eq. (2) results in e G2 = (873 K) + RT ln f2 e e G2 G1 = RT ln f2 f1 (1) (2) P ( bar) 50 0.1 b H ( kJ/ kg) 3666.5 3705.4 b S ( kJ/ kg. K) 7.2589 10.1608

(3)

or

e e e Note that Eq. (3) can also be obtained from Eq. (5.2-1). Since G = H T S, Eq. (3) becomes e e e e 2 H1 ) T (S2 S1 ) = RT ln f2 (4) (H f1 i h b b b b 2 H1 ) T (S2 S1 ) = RT ln f2 M (H f1 f1 = P1 = 0.1 bar 96 (5)

where M is the molecular weight of water. At 873 K and 0.1 bar, it is plausible to assume that steam behaves as an ideal gas, i.e.,

Substitution of the numerical values into Eq. (5) gives i f2 18 (3666.5 3705.4) (873)(7.2589 10.1608) = (8.314)(873) ln 0.1 h The solution yields f2 = 48.6 bar

5.3.3 Fugacity from the Virial Equation of State At low to moderate pressures, it is possible to truncate the virial equation of state after the second term as given by Eq. (3.1-9), i.e., ZiV = 1 + Bi P RT (5.3-4)

where Bi , the second virial coecient for pure i, is calculated from Eq. (3.1-10). Substitution of Eq. (5.3-4) into Eq. (5.3-2) and integration give ln V = i Bi P RT (5.3-5)

5.3.4 Fugacity from Cubic Equations of State e The cubic equations of state are pressure-explicit, i.e., P = P (V , T ), and the use of Eq. (5.3-1) is not practical for this case. Therefore, it is useful to have an equation relating fugacity to an integral over volume rather than pressure. For this purpose, the starting point is the equation of state for a real gas, i.e., e P Vi = ZiV RT (5.3-6)

At constant temperature, dierentiation of Eq. (5.3-6) gives e dVi dZiV dP = + V P e Zi Vi Z

e Vi

(5.3-7)

Substitution of Eqs. (5.3-6) and (5.3-7) into Eq. (5.3-2) yields 1 ln V = ZiV 1 ln ZiV + i RT RT e P dV e Vi

T = constant

(5.3-8)

Substitution of the cubic equation of state into Eq. (5.3-8) and integration lead to the following general expression for calculating fugacity coecients in the vapor phase: ln V = ZiV 1 ln(ZiV Bi ) V i i where the term V is given in Table 5.1 depending on the equation of state. i (5.3-9)

97

Table 5.1 The term V in Eq. (5.3-9)2 . i Equation of State van der Waals Ai ZiV ! Bi Ai ln 1 + V Bi Zi ! Ai Bi ln 1 + V Bi Zi " V # Zi + (1 + 2) Bi Ai ln V 8 Bi Zi + (1 2) Bi V i (A)

Redlich-Kwong

(B)

Soave-Redlich-Kwong

(C)

Peng-Robinson

(D)

Equation (5.3-9) can also be obtained by substituting departure function expressions developed in Section 3.6.1 into Eq. (5.2-1). Example 5.3 Calculate the fugacity coecient of acetylene at 373 K and 1, 10, and 50 bar if it obeys a) van der Waals equation of state, b) Redlich-Kwong equation of state, c) Soave-Redlich-Kwong equation of state, d) Peng-Robinson equation of state. Solution From Appendix A Tc = 308.3 K The reduced temperature is Tr = The values of the reduced pressures are P ( bar) Pr 1 0.016 10 0.163 50 0.814 T 373 = 1.210 = Tc 308.3 Pc = 61.4 bar = 0.190

a) For the van der Waals equation of state, the values of A, B, Z, and are given in the following table: P ( bar) 1 10 50
2

A 4.61 103 0.047 0.235

B 1.653 103 0.017 0.084

Z 0.997 0.969 0.830

0.997 0.970 0.852

The dimensionless parameters Ai and Bi can be calculated from the expressions given in Table 3.2.

98

b) For the Redlich-Kwong equation of state, the values of A, B, Z, and are given in the following table: P ( bar) 1 10 50

A 4.247 103 0.043 0.216

B 1.146 103 0.012 0.058

Z 0.997 0.968 0.833

0.997 0.969 0.850

c) For the Soave-Redlich-Kwong equation of state, the values of , A, B, Z, and are given in the following table: P ( bar) 1 10 50

0.853 0.853 0.853

A 3.985 103 0.041 0.203

B 1.146 103 0.012 0.058

Z 0.997 0.971 0.850

0.997 0.971 0.863

d) For the Peng-Robinson equation of state, the values of , A, B, Z, and are given in the following table: P ( bar) 1 10 50

0.873 0.873 0.873

A 4.362 103 0.044 0.222

B 1.029 103 0.010 0.052

Z 0.997 0.966 0.829

0.997 0.966 0.843

5.3.5 Fugacity from the Principle of Corresponding States In terms of reduced temperature and pressure, Eq. (5.2-1) takes the form ln V i e e e IG eIG (Si Si )T,P 1 (Hi Hi )T,P = Tr RTc R

(5.3-10)

in which the enthalpy and entropy departure functions are calculated from Eqs. (3.6-24) and (3.6-25), respectively. 5.4 FUGACITY OF A PURE LIQUID When liquid and vapor phases of a pure component i are in equilibrium with each other, the number of degrees of freedom is unity. In other words, the equilibrium state can be determined by specifying one independent intensive variable, for example, temperature. At any given temperature, the corresponding pressure is the vapor pressure (or saturation pressure), Pivap , as shown in Figure 5.2.

99

~ Gi

T = constant

Vapor

Liquid

Pivap

Figure 5.2 Variation of Gibbs energy with pressure at constant temperature. The vapor and liquid phases are in equilibrium with each other at the point of intersection e of Gi versus P curves in Figure 5.2. Thus, In other words, there is no variation in fugacity during a phase change, i.e., from liquid to vapor or vice versa. Using Eq. (5.2-5), molar Gibbs energy of a pure liquid at any temperature and pressure is expressed as ei (5.4-2) GL (T, P ) = i (T ) + RT ln fiL (T, P ) ei GL (T, Pivap ) = i (T ) + RT ln fiL (T, Pivap ) " " fiL (T, P ) fiL (T, Pi
vap

ei ei GV (T, Pivap ) = GL (T, Pivap )

fiV (T, Pivap ) = fiL (T, Pivap )

(5.4-1)

On the other hand, molar Gibbs energy of a pure liquid at the same temperature but at the corresponding vapor pressure is given by

(5.4-3)

Subtraction of Eq. (5.4-3) from Eq. (5.4-2) gives

The use of Eq. (5.4-1) in Eq. (5.4-4) leads to

ei ei GL (T, P ) GL (T, Pivap ) = RT ln

# #

(5.4-4)

At constant temperature, integration of Eq. (5.2-10) from Pivap to P yields ei ei e GL (T, P ) GL (T, Pivap ) = ViL (P Pivap ) " (5.4-6)

ei ei GL (T, P ) GL (T, Pivap ) = RT ln

fiL (T, P ) fiV (T, Pi

vap

(5.4-5)

in which the molar volume of liquid is considered constant. Substitution of Eq. (5.4-6) into Eq. (5.4-5) and rearrangement result in fiL (T, P ) fiV (T, Pivap ) exp e ViL (P Pivap ) RT #

(5.4-7)

100

or fiL (T, P ) = Pivap V i (T, Pivap ) exp

"

e ViL (P Pivap ) RT

(5.4-8)

The exponential term in Eqs. (5.4-7) and (5.4-8) is commonly referred to as the Poynting correction factor. It accounts for the compression of the liquid to a pressure P greater than its vapor pressure, Pivap . Table 5.2 indicates the variation in Poynting correction factor as a function of pressure. Examination of the values clearly reveals that the Poynting correction factor (PCF) is almost unity at low pressures but may become large at extremely high pressures or low temperatures. Table 5.2 Variation of the Poynting correction factor as a function of pressure and e temperature when V L = 50 cm3 / mol. T ( K) 298 298 298 300 100 50 P P vap ( bar) 1 100 1000 50 50 50 Poynting Correction Factor 1.002 1.224 7.524 1.105 1.351 1.825

Example 5.4 Specify the conditions under which the fugacity of liquid is almost equal to the vapor pressure at a given temperature, i.e., fiL (T, P ) ' Pivap . Solution When pressure is not very high, the Poynting correction factor is unity and Eq. (5.4-8) simplies to (1) fiL (T, P ) = Pivap V (T, Pivap ) i When the vapor pressure is not very high, the vapor phase may be considered an ideal gas and V (T, Pivap ) = 1. Thus, Eq. (1) becomes i fiL (T, P ) = Pivap (2)

Comment: Using steam tables, Rittmann et al. (1982) expressed the fugacity of saturated water and saturation pressure of water as
sat ln fH 2 O = 8.9672 vap ln PH 2 O = 13.8365 vap sat where fH 2 O and PH 2 O

1138.26 10.6317 105 8.8730 107 + T T2 T3

6.6075 103 10.1855 105 17.7039 107 + T T2 T3 are in bar, and T is in K. These equations are valid when 300 T 600

vap sat The calculated values of PH 2 O and fH2 O are given in the following table:

101

T ( K) 300 350 400 450 500

vap PH 2 O ( bar)

sat fH2 O ( bar)

0.032 0.425 2.503 9.395 26.560

0.035 0.413 2.392 8.760 23.496

Thus, at higher values of vapor pressure, the dierence between vapor pressure and fugacity becomes appreciable. Evaluation of liquid fugacities requires molar volumes of saturated liquids to be known. Molar volumes of various liquids as a function of temperature are given in Table 5.3. Table 5.3 Molar volumes of various liquids (Holmes and van Winkle, 1970). Substance T ( K) 228.15 273.15 323.15 273.15 303.15 355.15 273.15 323.15 373.15 273.15 343.15 413.15 293.15 353.15 413.15 273.15 303.15 333.15 288.15 306.30 352.35 273.15 323.15 373.15 273.15 323.15 373.15 e VL 3 / mol) ( cm 67.380 71.483 76.826 51.092 53.214 57.4 86.783 92.263 98.537 89.873 97.8 108.7 96.518 104.192 114.379 78.218 81.185 84.5 107.470 109.841 116.630 57.141 60.356 64.371 95.3 102.1 110.5 Substance T ( K) 273.15 323.15 373.15 273.15 323.15 373.15 273.15 373.15 473.15 273.15 333.15 373.15 273.15 333.15 393.15 273.15 333.15 373.15 293.15 343.15 393.15 303.15 353.15 400.00 277.13 323.15 373.15 e VL 3 / mol) ( cm 143.045 152.303 163.619 127.301 136.388 148.211 39.556 44.874 57.939 87.3 94.5 100.0 158.970 170.630 185.182 111.8 122.9 131.4 74.785 78.962 84.515 107.415 113.717 120.879 18.060 18.278 18.844

Acetone

n-Heptane

Acetonitrile

n-Hexane

Benzene

Methanol

n-Butanol

Methyl ethyl ketone

Carbon tetrachloride

n-Octane

Chloroform

n-Pentane

Cyclohexane

n-Propanol

Ethanol

Toluene

Ethyl acetate

Water

102

If experimental data are unavailable, molar volumes of saturated liquids can be estimated by the modied Rackett equation (Spencer and Danner, 1972) RTc 1+(1Tr )2/7 e Z VL = Pc RA (5.4-9)

where ZRA is the Rackett parameter, given by

ZRA = 0.29056 0.08775

(5.4-10)

Example 5.5 Estimate the molar volume of liquid carbon dioxide at 274 K and 70 bar using the Soave-Redlich-Kwong equation of state, the Peng-Robinson equation of state, and the Rackett equation. Solution From Appendix A Tc = 304.2 K Pc = 73.8 bar = 0.239 The values of the reduced temperature and pressure are Tr = 274 = 0.901 304.2 and Pr = 70 = 0.949 73.8

The molar volume is calculated from Z L RT e VL = P

For the Soave-Redlich-Kwong and Peng-Robinson equations of state the results are given in the following table: Equation of State Soave-Redlich-Kwong Peng-Robinson The Rackett parameter is ZRA = 0.29056 (0.08775)(0.239) = 0.270 The use of Eq. (5.4-9) gives (83.14)(304.2) 2/7 e (0.270)1+(10.901) = 47.1 cm3 / mol VL = 73.8 A 0.544 0.575 B 0.091 0.082 ZL 0.160 0.142 e V L ( cm3 / mol) 52.1 46.2

Comment: In general, the Soave-Redlich-Kwong equation of state overpredicts the liquid molar volume by 10% to 35%.

Example 5.6 Calculate the fugacity of benzene at 320 K and 100 bar. The vapor pressure of benzene at 320 K is 0.308 bar. 103

Solution From Appendix A Tc = 562 K Pc = 48.9 bar = 0.212 Since T < Tc and P > P vap , benzene exists as a liquid at the given temperature and pressure. Application of Eq. (5.4-8) gives
L fbenzene (320 K, 100 bar) = 0.308 V benzene (320 K, 0.308 bar) exp

"

eL Vbenzene (100 0.308) (83.14)(320)

(1)

Since the vapor pressure is low, vapor may be considered an ideal gas, i.e., V benzene (320 K, 0.308 bar) ' 1 From Table 5.3 eL Vbenzene ' 92.263 cm3 / mol

Substitution of the numerical values into Eq. (1) gives the liquid fugacity as (92.263)(100 0.308) L = 0.435 bar fbenzene (320 K, 100 bar) = 0.308 exp (83.14)(320) If liquid fugacity is known at (T, P1 ), the value of the liquid fugacity at (T, P2 ) can be calculated from Eq. (5.4-8) as fiL (T, P2 ) = fiL (T, P1 ) exp " e ViL (P2 P1 ) RT # (5.4-11)

5.4.1 Fugacity from Cubic Equations of State Since cubic equations of state can describe pure substances in both the vapor and liquid phases, Eq. (5.3-9) is also applicable to liquids, i.e., ln L = ZiL 1 ln(ZiL Bi ) L i i where the term L is given in Table 5.4 depending on the equation of state. i Example 5.7 Estimate the vapor pressure of ethanol at 313 K by using the condition of chemical equilibrium. Assume that ethanol is represented by the Peng-Robinson equation of state. Solution From Appendix A Tc = 514 K Pc = 63 bar = 0.644 The condition of equilibrium is given by Eq. (5.4-1), i.e.,
vap vap V L fethanol (T, Pethanol ) = fethanol (T, Pethanol )

(5.4-12)

(1)

104

Table 5.4 The term L in Eq. (5.4-12)3 . i Equation of State van der Waals Ai ZiL ! Ai Bi ln 1 + L Bi Zi ! Bi Ai ln 1 + L Bi Zi " L # Zi + (1 + 2) Bi Ai ln L 8 Bi Zi + (1 2) Bi L i (A)

Redlich-Kwong

(B)

Soave-Redlich-Kwong

(C)

Peng-Robinson

(D)

vap Dividing Eq. (1) by Pethanol gives vap vap L V ethanol (T, Pethanol ) = ethanol (T, Pethanol )

(2)

An algorithm to estimate the vapor pressure at a given temperature is given as follows: 1. 2. 3. 4. 5. 6. 7. Obtain Tc , Pc , and from Appendix A, Determine the reduced temperature, Use Eq. (3.1-16) to determine the term , vap Assume Pethanol and determine the reduced pressure, Determine the dimensionless parameters A and B (Table 3.2), Evaluate the parameters p, q, and r appearing in Eq. (3.1-18) (Table 3.2), Solve Eq. (3.1-18), i.e., Z 3 + p Z 2 + q Z + r = 0. The largest and the smallest roots correspond to Z V and Z L , respectively. L 8. Use Z V in Eq. (5.3-9) and calculate V ethanol . Use Z in Eq. (5.4-12) and calculate L V L ethanol . Repeat steps (4)-(8) until ethanol = ethanol . Tr =

The reduced temperature is T 313 = 0.609 = Tc 514 The term is calculated from Eq. (3.1-16) as i2 h = 1.628 = 1 + 0.37464 + (1.54226)(0.644) (0.26992)(0.644)2 1 0.609 The results of the iterative procedure are given below:
vap Pethanol ( bar)

0.1 0.2 0.1888

A 103 3.186 6.372 6.015

B 104 2.028 4.056 3.829

Z L 104 2.379 4.759 4.492

ZV 0.997 0.994 0.994

L 1.877 0.939 0.994

V 0.997 0.994 0.994

Therefore, the vapor pressure of ethanol at 313 K is 0.1888 bar (or 141.6 mmHg). In other words, ethanol exists in liquid form at 313 K when P > 0.1888 bar.
3

The dimensionless parameters Ai and Bi can be calculated from the expressions given in Table 3.2.

105

5.5 FUGACITY OF A PURE SOLID When solid and vapor phases of a pure component i are in equilibrium with each other, the number of degrees of freedom is unity. In other words, the equilibrium state can be determined by specifying one independent intensive variable, for example temperature. At any given temperature, the corresponding pressure is the sublimation pressure (or vapor pressure), Pisub , as shown in Figure 5.3.
~ Gi

T = constant

Vapor

Solid

Pisub

Figure 5.3 Variation of Gibbs energy with pressure at constant temperature. The vapor and solid phases are in equilibrium with each other at the point of intersection e of Gi versus P curves in Figure 5.3. Thus, Using Eq. (5.2-5), molar Gibbs energy of a pure solid at any temperature and pressure is expressed as ei (5.5-2) GS (T, P ) = i (T ) + RT ln fiS (T, P ) ei GS (T, Pisub ) = i (T ) + RT ln fiS (T, Pisub ) = RT ln " " fiS (T, P ) fiS (T, Pi
sub

ei ei GV (T, Pisub ) = GS (T, Pisub )

fiV (T, Pisub ) = fiS (T, Pisub )

(5.5-1)

On the other hand, molar Gibbs energy of a pure solid at the same temperature but at the corresponding sublimation pressure is given by

(5.5-3)

Subtraction of Eq. (5.5-3) from Eq. (5.5-2) gives ei ei GS (T, P ) GS (T, Pisub )

# #

(5.5-4)

The use of Eq. (5.5-1) in Eq. (5.5-4) leads to

At constant temperature, integration of Eq. (5.2-10) from Pisub to P yields ei ei e GS (T, P ) GS (T, Pisub ) = ViS (P Pisub ) 106 (5.5-6)

ei ei GS (T, P ) GS (T, Pisub )

= RT ln

fiS (T, P ) fiV (T, Pi

sub

(5.5-5)

Substitution of Eq. (5.5-6) into Eq. (5.5-5) and rearrangement result in " S # e Vi (P Pisub ) fiS (T, P ) = Pisub V T, Pisub exp i RT

(5.5-7)

Sublimation pressure of solids is normally low. Therefore, ideal gas behavior for the gas phase over the pure solid can be assumed, i.e., V T, Pisub ' 1, and Eq. (5.5-7) simplies to i fiS (T, P ) = Pisub exp " e ViS (P Pisub ) RT # (5.5-8)

If solid fugacity is known at (T, P1 ), the value of solid fugacity at (T, P2 ) can be calculated from Eq. (5.5-8) as " # e ViS (P2 P1 ) fiS (T, P2 ) = fiS (T, P1 ) exp (5.5-9) RT Example 5.8 Calculate the fugacity of ice at 250 K and 100 bar using the following data:
sub ln Pice ( bar) =

2378.6 + 51.06 ln T 0.225 T + 1.62 104 T 2 233.45 T

Solution At 250 K

e Vice ( cm3 / mol) = 19.655 + 0.0022364 (T 273.15)

sub Pice = 7.743 104 bar

and

The use of Eq. (5.5-8) gives fice = 7.743 10

4

(19.603)(100) = 8.51 104 bar exp (83.14)(250)

e Vice = 19.603 cm3 / mol

5.6 PHASE TRANSITIONS AND EQUILIBRIUM CRITERIA The pressure-temperature diagram of a pure component includes three curves representing liquid-vapor, solid-vapor, and liquid-solid equilibrium as shown in Figure 5.4. Such plots are also referred to as the phase diagrams. When P < Pc , a substance in the gaseous state is called either a gas (T > Tc ) or a vapor (T < Tc ). Under isothermal conditions, while a vapor can be liqueed by exerting pressure, a gas cannot be liqueed no matter what pressure is applied to it. The triple point is the only point on the phase diagram where the solid, liquid, and vapor phases coexist in equilibrium4 . In other words, it is the intersection of the liquid-vapor (vapor pressure curve), solid-liquid (fusion or melting curve), and solid-vapor (sublimation pressure curve) coexistence curves. Note that the number of degrees of freedom, F , is zero at the triple point. Triple point temperatures and pressures of some substances are given in Table 5.5. If the
In general, the triple point is the point of intersection of three dierent phases. If a substance exists in dierent forms of solid, e.g., graphite and diamond for carbon, it can have more than one triple point.
4

107

Solid line normal subs tan ces Fusion curve Dashed line water FLUID SOLID LIQUID Critical point GAS Triple point Vaporization curve VAPOR Sublimation curve T

Figure 5.4

Temperature-pressure diagram.

Table 5.5

Normal boiling point, normal melting point, and triple point temperature and pressure for various substances5 . Temperature ( C) at P = 1 atm Triple Point T ( C) 77.74 7.25 56.57 80.27 75.47 0.01 P ( atm) 0.06 0.058 5.1172 0.0099 0.0165 0.006 Boiling Point 33.33 58.75 78.45 217.99 10.05 100 Melting (Freezing) Point 77.74 7.25 56.57 80.15 75.55 0

Substance Ammonia Bromine Carbon dioxide Naphthalene Sulfur dioxide Water

triple point pressure is less than 1 atm, as in the case of water, it is possible to have all three phases of a substance under atmospheric pressure depending on temperature. If the triple point pressure is higher than 1 atm, as in the case of carbon dioxide, then a substance cannot exist in the liquid form under atmospheric pressure, and the transition from the solid to vapor form, i.e., sublimation, takes place with an increase in temperature. At temperatures and pressures higher than the critical values, substances exist in the uid (or supercritical) region and are called supercritical uids. They possess both the gaseous properties (viscosity, diusivity, surface tension) of being able to diuse into substances easily, and the liquid property (density) of being able to dissolve substances. The slope of the vaporization curve gives the rate of change of vapor pressure of liquid with temperature. The slope of the sublimation curve gives the rate of change of sublimation (or vapor) pressure of solid with temperature. Finally, the slope of the fusion (or melting) curve gives the rate of change of the melting (or freezing) pressure of solid with temperature. While the fusion curve has a positive slope for most substances, the slope becomes negative for water. Since the fusion curve generally has a very steep slope, the triple point temperature for most substances is close to their melting (or freezing) temperature at atmospheric pressure, known as normal melting (or freezing) temperature.
5

Compiled from Korea Thermophysical Properties Data Bank (www.cheric.org/research/kdb).

108

Phase diagrams can also be expressed in the form of pressure versus specic volume as shown in Figure 5.5. Contrary to the case of the pressure versus temperature diagram, transition from one phase to another is shown in the form of area.
P

Pc SOLID + LIQUID LIQUID

GAS

SOLID

VAPOR

Tc

LIQUID + VAPOR
Isotherms
Triple point

Pt

SOLID + VAPOR V

Figure 5.5 Pressure-specic volume diagram.

5.6.1 Clapeyron Equation The starting point for obtaining quantitative information on the slopes of these equilibrium curves, i.e., dP/dT , is the fact that molar Gibbs energies of the phases are equal to each other e e G = G (5.6-1)

where subscripts and represent dierent phases. The dierential form of Eq. (5.6-1) is e e dG = dG (5.6-2)

The use of Eq. (5.1-1) in Eq. (5.6-2) leads to

Rearrangement of Eq. (5.6-3) yields

e e e e V dP S dT = V dP S dT dP dT = e e S S e e V V

(5.6-3)

(5.6-4)

eq

where the subscript eq indicates that the path of integration is on the vaporization curve, the fusion curve, or the sublimation curve. The entropy dierence in Eq. (5.6-4) must be expressed in terms of measurable quantities. e e e For this purpose, the use of the identity G = H T S in Eq. (5.6-1) leads to e e e e H T S = H T S e e H H e e S S = T (5.6-5)

109

Substitution of Eq. (5.6-5) into Eq. (5.6-4) gives dP dT = e e H H (5.6-6)

eq

which is known as the Clapeyron6 equation. 5.6.2 Vapor-Liquid Equilibrium

e e T (V V )

The amount of heat to convert saturated liquid to saturated vapor is called the enthalpy change e on vaporization or simply the heat of vaporization, H vap . If the -phase is considered to be vapor and the -phase to be liquid, then and e e e e e H H = H V H L = H vap

(5.6-7)

e e e e e V V = V V V L ' V V RT = vap if the vapor is an ideal gas P Substitution of Eqs. (5.6-7) and (5.6-8) into Eq. (5.6-6) results in e dP vap H vap dT = R T2 P vap e H vap d ln P vap = dT RT 2

(5.6-8)

(5.6-9)

or

(5.6-10)

which is referred to as the Clausius7 -Clapeyron equation. Integration of Eq. (5.6-10) depends e on whether H vap is constant or changes with temperature. e When H vap is constant, Eq. (5.6-10) can be rearranged as e 1 H vap vap d = d ln P R T Integration of Eq. (5.6-11) gives ln P vap = e H vap +C RT e H vap is independent of temperature

(5.6-11)

(5.6-12)

where C is an integration constant. Equation (5.6-12) indicates that a plot of ln P vap versus e 1/T is a straight line with a slope equal to ( H vap /R). Between any two states 1 and 2 on the vapor pressure curve, Eq. (5.6-12) yields vap ! P2 e 1 1 H vap ln (5.6-13) = vap R T2 T1 P
1

which provides accurate estimates of vapor pressures only over small temperature ranges.
6 7

Benoit Paul Emile Clapeyron, French engineer and physicist. Rudolf Julius Emanuel Clausius, German physicist and mathematician.

110

e The variation of H vap with temperature is expressed in the form Integration of Eq. (5.6-14) gives

e H vap varies with temperature

e e e dH vap dH V dH L eV eL eV = = CP CP = CP L dT dT dT e H vap = Z
T

(5.6-14)

Tref

e vap e e where Href is the value of H vap at the reference temperature, Tref . Once H vap is expressed as a function of temperature from Eq. (5.6-15), substitution of the resulting expression into Eq. (5.6-10) and integration yield the relationship between vapor pressure and temperature. eV If CP L is independent of temperature, then Eq. (5.6-15) reduces to Substitution of Eq. (5.6-16) into Eq. (5.6-10) and integration yield ! ! eV e vap eV Href CP L Tref 1 CP L +C ln P vap = ln T R R T eV e vap e H vap = CP L (T Tref ) + Href (5.6-16)

eV e vap CP L dT + Href

(5.6-15)

(5.6-17)

where C is an integration constant. In the literature, among the various equations relating vapor pressure to temperature, the most widely used is the Antoine equation, expressed in the form ln P vap = A B T +C (5.6-18)

The constants A, B, and C are given in Appendix C. Note that when C = 0, Eq. (5.6-18) reduces to Eq. (5.6-12). Example 5.9 Calculate the heat of vaporization of n-heptanol [CH3 (CH2 )6 OH] at the normal boiling temperature. Solution From Appendix C ln P vap = 8.6866 2626.42 T 146.6 (1)

At the normal boiling temperature, the vapor pressure of liquid equals 1 atm ( 1.013 bar). Therefore, the normal boiling temperature can be calculated from the Antoine equation as ln 1.013 = 8.6866 2626.42 T 146.6 T = 449.4 K

The heat of vaporization can be determined from Eq. (5.6-10). Dierentiation of Eq. (1) with respect to temperature gives 2626.42 d ln P vap = (2) dT (T 146.6)2 111

Thus, comparison of Eq. (2) with Eq. (5.6-10) results in e H vap 2626.42 = 2 RT (T 146.6)2 e H vap = 2626.42 RT 2 (2626.42)(8.314)(449.4)2 = = 48, 098 J/ mol (T 146.6)2 (449.4 146.6)2

or

5.6.3 Solid-Liquid Equilibrium e The amount of heat required to melt a solid is called the heat of fusion, H f us . If the -phase is considered to be liquid and the -phase to be solid, then e The volume change on melting, V f us , is given by e e e e e H H = H L H S = H f us > 0 e e e V f us = V L V S e dP H f us = dTm e Tm V f us (5.6-19)

(5.6-20)

Therefore, the slope of the solid-liquid equilibrium curve, i.e., Eq. (5.6-6), becomes (5.6-21)

e where Tm is the melting temperature. Since H f us > 0, the slope of the solid-liquid equilibrium e curve is either positive or negative depending on the sign of V f us . For almost all substances e f us > 0 and thus the slope of the solid-liquid equilibrium curve has a positive slope. Water V is an exception as the density of ice, 917 kg/ m3 , is less than that of liquid water, 1000 kg/ m3 . In this case 1 1 e f us = 18 = 1.63 103 m3 / kmol V 1000 917 and the slope of the solid-liquid equilibrium curve is negative. e Integration of Eq. (5.6-21) depends on whether H f us is constant or changes with temperature. e H f us is independent of temperature e When H f us is constant, integration of Eq. (5.6-21) gives ! e H f us P = ln Tm + C e V f us

(5.6-22)

Example 5.10 Explain quantitatively why a 55 kg ice skater glides on solid ice but not on e dry ice (solid CO2 ) under atmospheric conditions? For water H f us = 6012 kJ/ kmol. 112

where C is an integration constant. Between any two states 1 and 2 on the solid-liquid equilibrium curve, Eq. (5.6-22) yields ! b f us ! e Tm2 Tm2 H f us H = (5.6-23) ln ln P2 P1 = Tm1 Tm1 e b V f us V f us

Solution The normal melting (or freezing) temperature of water is 0 C. If the length and the thickness of the skating blade are 150 mm and 3 mm, respectively, then the pressure exerted by the weight of the skater is P = (55)(9.8) mg = = 1.198 106 Pa = 1.198 103 kPa A (150 103 )(3 103 )

The decrease in the melting temperature leads to liquefaction of water, which in turn acts as a lubricating layer during skating. In the case of dry ice, on the other hand, dP/dTm is positive and the melting temperature increases with increasing pressure. As a result, carbon dioxide remains as a solid. Comment: Melting under pressure and refreezing again with a release of pressure is known as "regelation". Another typical example of this phenomenon is the movement of a weighted wire through an ice block without cutting it into two pieces. The applied pressure lowers the melting temperature of ice and a lm of water forms. As the wire moves downward, the release of pressure on the meltwater causes refreezing of the melted portion. e H f us varies with temperature

As a result of the increase in pressure, the melting temperature can be calculated from Eq. (5.6-23) as " # ! e V f us Tm2 = Tm1 exp (P2 P1 ) e H f us 1.63 103 3 = 273 exp 1.198 10 101.3 = 272.92 K 6012

e The variation of H f us with temperature is expressed in the form Integration of Eq. (5.6-24) gives

e e e dH L dH S dH f us eL eS eLS = = CP CP = CP dT dT dT e H f us = Z
Tm Tref

(5.6-24)

e f us e e where Href is the value of H f us at the reference temperature, Tref . Once H f us is expressed as a function of melting temperature from Eq. (5.6-25), substitution of the resulting expression into Eq. (5.6-21) and integration yield the relationship between pressure and melting temperature on the solid-liquid equilibrium curve. eLS If CP is independent of temperature, then Eq. (5.6-25) reduces to Substitution of Eq. (5.6-26) into Eq. (5.6-21) and integration yield ! e f us eLS Href CP Tref eLS P = CP Tm + ln Tm + C e V f us 113 eLS e f us e H f us = CP (Tm Tref ) + Href (5.6-26)

eLS e f us CP dT + Href

(5.6-25)

(5.6-27)

where C is an integration constant.

Example 5.11 The normal melting temperature of lead (atomic weight = 207) is 600.65 K and the enthalpy of fusion is 4812 J/ mol. Estimate the melting temperatures of lead at 50, 100, 150, and 200 bar using the following data: L = 10, 215 kg/ m3 eL CP = 32.4 3.1 103 T S = 11, 350 kg/ m3 eS CP = 23.6 + 9.75 103 T

e where CP is in J/ mol. K and T is in K. Solution

The dierence between the heat capacities of liquid and solid is eLS CP = 8.8 12.85 103 T (1)

e The volume change on melting, V f us , is given by 1 1 e 207 = 2.0264 103 m3 / kmol = 2.0264 106 m3 / mol V f us = 10, 215 11, 350 Thus, substitution of Eqs. (2) and (3) into Eq. (5.6-21) and integration result in Z Tm 8.8 T 6.425 103 T 2 + 1844.3 1 dT (P 1.013) 105 = 2.0264 106 600.65 T
2 P = 43.427 Tm + 9101.4 ln Tm 1.5853 102 Tm 78, 594

e f us Taking Tref = 600.65 K and Href = 4812 J/ mol, substitution of Eq. (1) into Eq. (5.6-25) gives e (2) H f us = 8.8 T 6.425 103 T 2 + 1844.3 (3)

Simplication gives (4)

Melting temperatures calculated at dierent pressures are given in the table below. P ( bar) Tm ( K) 50 601.9 100 603.1 150 604.4 200 605.7

5.6.4 Solid-Vapor Equilibrium e The amount of heat required to convert solid to vapor is called the heat of sublimation, H sub . In general, heat of sublimation is indirectly determined from heat of vaporization and heat of fusion as e e e e e e e e e H sub = H V H S = (H V H L ) + (H L H S ) = H vap + H f us e e e e V sub = V V V S ' V V RT = sub if the vapor is an ideal gas P 114 (5.6-28)

The volume change on sublimation is given by

(5.6-29)

Thus, the slope of the solid-vapor equilibrium line, i.e., Eq. (5.6-6), becomes e d ln P sub H sub = dT RT 2 (5.6-30)

e e which is similar to Eq. (5.6-19). Since H sub > H vap , the slope of the sublimation curve is steeper than that of the vaporization curve. e If H sub is independent of temperature, integration of Eq. (5.6-30) gives ln P sub = e H sub +C RT

(5.6-31)

The constant of integration in Eq. (5.6-31), C, can be evaluated using the triple point data as C= e H sub + ln Pt RTt (5.6-32)

where Pt and Tt represent triple point pressure and temperature, respectively. Substitution of Eq. (5.6-32) into Eq. (5.6-31) gives ln P sub Pt e H sub = R 1 1 T Tt (5.6-33)

5.7 ANALYSIS OF PHASE DIAGRAMS USING STABILITY CRITERIA It was stated in Section 4.3 that a substance, at a given temperature and pressure, is most stable in a phase in which its Gibbs energy is minimum. For example, under normal conditions, i.e., 298 K and 1 bar (0.1 MPa), the dierence between the Gibbs energies of graphite and diamond is given as e e Gdiamond (298 K, 105 Pa) Ggraphite (298 K, 105 Pa) = 2870 J/ mol

e e Since Ggraphite < Gdiamond , graphite is the more stable phase under these conditions. If it is desired to produce diamond from graphite at room temperature, what should be the minimum pressure imposed for such a transformation? The starting point for answering such a question is the fact that spontaneous transition from graphite to diamond takes place when the two phases are in equilibrium with each other, i.e., e e (5.7-1) Gdiamond (298 K, P ) = Ggraphite (298 K, P ) At constant temperature, Eq. (5.1-1) gives the variation of Gibbs energy with pressure as e e dG = V dP e e e Gdiamond (298 K, P ) = Gdiamond (298 K, 105 Pa) + Vdiamond (P 105 ) (5.7-2)

Therefore,

(5.7-3) (5.7-4)

Substitution of Eqs. (5.7-3) and (5.7-4) into Eq. (5.7-1) and simplication lead to P = 105 + e e Gdiamond (298 K, 105 Pa) Ggraphite (298 K, 105 Pa) e e Vgraphite Vdiamond 115 (5.7-5)

e e e Ggraphite (298 K, P ) = Ggraphite (298 K, 105 Pa) + Vgraphite (P 105 )

The densities of graphite and diamond are approximately 2300 and 3530 kg/ m3 , respectively. Thus, substitution of the numerical values into Eq. (5.7-5) gives P = 105 + 2870 103 = 1.58 109 Pa 1 1 (12) 2300 3530

Thus, at room temperature, graphite can be converted into diamond when P 1580 MPa. 5.7.1 Gibbs-Helmholtz Equation e In some cases, it is much more convenient to determine the variation of G/T with temperature under constant pressure. Mathematically speaking, we are interested in ! ! e e e 1 G G G = 2 (5.7-6) T T T T T
P P

From Eq. (5.1-1)

Substitution of Eq. (5.7-7) into Eq. (5.7-6) gives T

e G T

e = S

(5.7-7)

! e e H G = 2 T T
P

(5.7-8)

which is known as the Gibbs-Helmholtz equation. Example 5.12 Estimate the normal melting temperature of lead using the following data:

P ( bar) 1.013 1.013

T ( K) 400 1200

Phase Solid Liquid

e H ( J/ mol) 2770 31, 160

e S ( J/ mol. K) 72.8 113.1

The heat capacities at constant pressure are given by eS CP = 23.6 + 9.75 103 T and eL CP = 32.4 3.1 103 T

e where CP is in J/ mol. K and T is in K. Solution

A representative phase diagram of lead is shown below. At the normal melting temperature, Tm , solid and liquid phases are in equilibrium with each other (State B), i.e., e e GS GL Tm Tm = (1) Tm Tm 116

P S 1.013 bar A B C L

400 K

Tm

1200 K

At constant pressure, Eq. (5.7-8) is expressed in the form ! e e G H d = 2 dT T T e dH e = CP dT e H S = 23.6 T + 4.875 103 T 2 + C1

(2)

Integration of Eq. (2) requires the enthalpy to be expressed as a function of temperature, i.e., (3)

For the solid phase e dH S = 23.6 + 9.75 103 T dT

From the value of enthalpy at 400 K, the integration constant C1 is evaluated as 7450. Thus Substitution of Eq. (4) into Eq. (2) and integration from 400 K to Tm give e GS Tm 7450 = 96.1 23.6 ln Tm 4.875 103 Tm Tm Tm For the liquid phase e dH L = 32.4 3.1 103 T dT e H L = 32.4 T 1.55 103 T 2 + C2 e H S = 23.6 T + 4.875 103 T 2 7450 (4)

(5)

Since the value of enthalpy at 1200 K is known, the integration constant C2 is evaluated as 5488. Thus, e (6) H L = 32.4 T 1.55 103 T 2 5488 Substitution of Eq. (6) into Eq. (2) and integration from Tm to 1200 K give e GL Tm 5488 = 145.3 32.4 ln Tm + 1.55 103 Tm Tm Tm 1962 8.8 ln Tm + 6.425 103 Tm = 0 Tm 117 (7)

Substitution of Eqs. (5) and (7) into Eq. (1) and simplication lead to 49.2 + (8)

The solution of Eq. (8) by MATHCAD

gives Tm = 602.3 K.

Comment: The actual value of the normal melting temperature of lead is 600.65 K as given in Example 5.11.

5.8 VARIATION OF FUGACITY WITH PRESSURE AND TEMPERATURE Variation of fugacity with pressure under isothermal conditions can be easily obtained from Eq. (5.2-7) as ! e e ln fi Vi 1 Gi = = (5.8-1) P RT P RT T | {z T }
e Vi

On the other hand, dierentiation of Eq. (5.2-1) with respect to temperature by keeping pressure constant gives ! e e Gi GIG ln fi 1 i = (5.8-2) T R T T P
P

The use of the Gibbs-Helmholtz equation, Eq. (5.7-8), in Eq. (5.8-2) yields ln fi T e e Hi HiIG RT 2

(5.8-3)

e e Note that the term (Hi HiIG ) is simply the departure function for molar enthalpy. Variation in ln fi is expressed in the form of an exact dierential as ln fi ln fi d ln fi = dP + dT P T T P Substitution of Eqs. (5.8-1) and (5.8-3) into Eq. (5.8-4) gives e Vi RT ! e e Hi HiIG RT 2 !

(5.8-4)

d ln fi =

dP

dT

(5.8-5)

Example 5.13 Use Eq. (5.8-5) to express the fugacity of pure solid in terms of the fugacity of pure liquid. Solution For a liquid, Eq. (5.8-5) takes the form L! ! L e e e Vi Hi HiIG d ln fiL = dT dP RT RT 2 For a solid, on the other hand, Eq. (5.8-5) becomes S! ! S e e e Vi Hi HiIG d ln fiS = dT dP RT RT 2 118

(1)

(2)

Subtraction of Eq. (1) from Eq. (2) gives S! e e Hif us Vif us fi dP + d ln dT = L RT RT 2 fi

(3)

Integration of Eq. (3) from the normal melting temperature, Tmi , to T , and from 1 atm ( 1 bar) to P , under the assumption that the heat of fusion is a constant leads to S! e e Vif us (P 1) Hif us fi Tmi + (4) 1 = ln L RT RTmi T fi Since the dierence between the liquid and solid molar volumes is usually negligible, it is plausible to neglect the rst term on the right-hand side of Eq. (4) without loss of accuracy. Hence, Eq. (4) simplies to S! e Hif us fi Tmi ln (5) 1 = L RTmi T fi Comment: Equation (5) will be derived in Section 12.1 using a dierent approach.

REFERENCES Bignell, N. and V.E. Bean, 1988, Metrologia, 25, 141-145. Brunetti, B., V. Piacente and G. Portalone, 2000, J. Chem. Eng. Data, 45, 242-246. Douglas, T.B., 1948, J. Am. Chem. Soc., 70 (6), 2001-2002. Holmes, M.J. and M. van Winkle, 1970, Ind. Eng. Chem., 62 (1), 21-31. Lee, B. and W.C. Edmister, 1971, Ind. Eng. Chem. Fundam., 10 (2), 229-236. Rittmann, B., H. Knapp and J.M. Prausnitz, 1982, Ind. Eng. Chem. Process Des. Dev., 21, 695-698. Spencer, C.F. and R.P. Danner, 1972, J. Chem. Eng. Data, 17, 236-241. Stein, S.E. and R.L. Brown, 1994, J. Chem. Inf. Comput. Sci., 34, 581-587. Trouton, F.T., 1883, Nature, 27, 292. PROBLEMS Problems related to Section 5.3 5.1 Derive Eq. (5.3-9) by substituting the van der Waals equation of state into Eq. (5.3-8). 5.2 Use Eq. (5.3-2) and calculate the fugacity coecient of dimethyl ether at 420 K and 50 bar using the following data: P ( bar) Z 1 0.994 5 0.969 10 0.937 15 0.905 20 0.871 25 0.836 30 0.799 35 0.761 40 0.721 45 0.678 50 0.631

(Answer: 0.72) 119

5.3 Calculate the fugacity of propylene at 400 K and 50 bar if it obeys a) van der Waals equation of state, b) Redlich-Kwong equation of state, c) Peng-Robinson equation of state. (Answer: a) 37.207 bar b) 36.597 bar c) 35.741 bar) 5.4 Calculate the fugacity of propane at 390 K and 30 bar if it obeys a) Soave-Redlich-Kwong equation of state, b) Peng-Robinson equation of state. (Answer: a) 24.141 bar b) 23.558 bar) 5.5 Using the following data for the fugacity coecient of isobutane as a function of pressure at 500 K, estimate its molar volume at 500 K and 75 bar. P ( bar) 0 10 20 30 (Answer: 349.3 cm3 / mol) 5.6 In Example 5.2, Eq. (3) indicates that the change in Gibbs energy under isothermal conditions is given by e e2 G1 = RT ln f2 (1) G f1 f (Ws )rev = RT ln f2 f1 (2) C4 H 10 1.000 0.947 0.896 0.848 P ( bar) 40 50 60 70 C4 H 10 0.803 0.761 0.722 0.686 P ( bar) 80 90 100 C4 H 10 0.653 0.624 0.599

Combine Eq. (1) with Eq. (2.1-5) to show that

which can be used to estimate the work interaction of a steady-ow system under reversible and isothermal conditions. Carbon dioxide is compressed in a reversible isothermal steady-state ow process from 3 bar and 350 K to 70 bar. Determine the work of compression per mole of carbon dioxide using the Peng-Robinson equation of state. (Answer: 8509 J/ mol) Problems related to Section 5.4 5.7 Estimate the fugacity of 1-octene at 480 K and 12 bar if it obeys the virial equation of state. The vapor pressure of 1-octene at 480 K is 6.791 bar. (Answer: 5.919 bar) 5.8 Estimate the pressure at which the fugacity of liquid ethanol at 293 K is 5% higher than the fugacity of liquid at its saturation pressure. (Answer: 23.5 bar) 120

5.9 Use the condition of vapor-liquid equilibrium and estimate the temperature of saturated liquid water at 4.5 bar by using the Peng-Robinson equation of state. Compare the result with the one obtained from the following equation:
vap ln PH2 O = 13.8365

6.6075 103 10.1855 105 17.7039 107 + T T2 T3

300 T 600

vap in which PH 2 O is in bar and T is in K. (Answer: 421.56 K)

5.10 Estimate the vapor pressure of ethylene at 240 K using the van der Waals equation of state. (Answer: 25.5 bar) 5.11 Estimate the vapor pressure of liquid methane at 150 K using the Redlich-Kwong equation of state. (Answer: 10.1 bar) Problem related to Section 5.5 5.12 Pure A exists in solid-vapor equilibrium in a rigid container at 150 K and 10 bar. Calculate the fugacity of pure solid if the vapor phase is described by the virial equation of state, i.e., BP Z =1+ RT 5 m3 / mol. where B = 45 10 (Answer: 14.35 bar) Problems related to Section 5.6 5.13 Consider transformation of saturated liquid to saturated vapor at constant temperature and pressure by the addition of heat. e a) Show the process on a P -V diagram. b) Show the process on a P -T diagram. c) Which plot is more informative for the given process? Explain. 5.14 A portion of the phase diagram of sulfur is shown below. There are two solid phases of sulfur, rhombic and monoclinic. The standard Gibbs energy of formation of rhombic sulfur is 0 kJ/ mol and that of monoclinic sulfur is 0.33 kJ/ mol at 25 C. a) On the phase diagram, label the four regions and indicate the triple points. b) Is it possible to completely melt rhombic sulfur at 200 C? If no, explain the reason clearly. If yes, what pressure should be imposed on rhombic sulfur? c) It is required to convert rhombic sulfur to monoclinic sulfur and your friend suggests the following options: i) Heat rhombic sulfur at 1 atm, ii) Heat rhombic sulfur at 1 106 atm, iii) Heat rhombic sulfur at 9 103 atm iv) Decrease the pressure on rhombic sulfur at 65 C, v) Decrease the pressure on rhombic sulfur at 140 C, vi) Decrease the pressure on rhombic sulfur at 100 C. 121

Which one(s) of these processes is possible?

10 10 10 10 Pressure (atm )
4 3 2 1

1 10 10 10 10
-1 -2 -3 -4

10-5 10-6 40 60 80 100 120 140

o

160

180

200

Temperature ( C)

5.15 Troutons rule (Trouton, 1883) states that the entropy of vaporization of liquids at their normal boiling temperature, Tnb , is constant, i.e., e S vap = e H vap = 88 J/ mol. K Tnb (1)

It should be kept in mind that Troutons rule is an empirical relation and is not valid for hydrogen-bonded liquids. a) Show that the combination of Troutons rule with the Clausius-Clapeyron equation leads to 10.6 vap vap T2 P2 = P1 (2) T1

b) The normal boiling temperature of acetone is 56.5 C. Calculate the vapor pressure of acetone at various temperatures using Eq. (2) and compare the values with the ones given in the literature.

5.16 An improved version of Troutons rule, known as the Trouton-Hildebrand-Everett rule, is given by e H vap e = R (4 + ln Tnb ) (1) S vap = Tnb The vapor pressure of chloroform at 323.15 K is 0.703 bar. Use Eq. (1) to estimate the normal boiling temperature of chloroform. The experimental value is 334.3 K. (Answer: 335.2 K) 5.17 As stated in Problem 3.13, an isotherm representing the cubic equation of state satises the following equation: Z VV e vap e V e L) = e P dV (1) P (V V a) Dierentiate Eq. (1) with respect to temperature to obtain Z VV e P dP vap e V e e (V V L ) = dV dT T V e e VL 122
e VL

(2)

Hint: Use Leibnitzs rule to dierentiate the right-hand side of Eq. (1).

b) Combine Eq. (2) with the Clapeyron equation and show that H e vap =T Z
e VV

e e) Estimate H vap for saturated benzene at 298.15 K if it obeys the Redlich-Kwong equation of state. (Answer: e) 32.65 kJ/ mol) 5.18 Consider vapor-liquid equilibrium of a pure component. e a) Use P V = ZRT and show that Eq. (5.6-6) takes the form e dP vap H vap dT = vap P R Z vap T 2

d) For the Redlich-Kwong equation of state, show that the integration of the right-hand side of Eq. (3) leads to " ! # e e e e ZV B Z V (Z L + B) A H vap = ln ln + (5) RT 2B e e e ZL B Z L (Z V + B)

c) For the van der Waals equation of state, show that the integration of the right-hand side of Eq. (3) leads to ! e e ZV B H vap = ln (4) RT e ZL B

e VL

P T

e V

e dV

(3)

(1)

where Z vap = Z V Z L . e b) Assume H vap /Z vap to be a constant and show that the integration of Eq. (1) from the critical pressure, Pc , to any pressure, P vap , leads to vap e P H vap 1 log = 1 (2) Pc 2.303 R Z vap Tc Tr c) Use Eq. (3.1-14) and show that e H vap 7 = ( + 1) vap T 2.303 R Z 3 c

(3)

d) Combine Eqs. (2) and (3) to get vap 1 7 P = (1 + ) 1 log Pc 3 Tr which can be used to estimate vapor pressures of liquids when Tr 0.6.

(4)

e) Estimate the vapor pressure of carbon dioxide at 273.16 K using Eq. (4) and compare it with the literature value of 34.86 bar (Bignell and Bean, 1988). 5.19 Calculate the normal boiling temperature of n-propanol by the following two methods. a) Use vapor pressure data in the form of the Antoine equation. b) One way of estimating chemical and physical properties of pure compounds is the socalled group contribution method, which is based on the molecular structure of a compound. 123

The property in question is estimated by the additive contributions of the functional groups constituting the molecule. To estimate normal boiling temperatures, Tnb , of pure compounds, Stein and Brown (1994) proposed the following formula: X ni gi (1) Tnb ( K) = 198.2 +
i

where ni is the number of groups of type i in the molecule and gi is the contribution of each group. The normal boiling temperature predicted by Eq. (1) must be corrected by the following equations: 2 1.5577 Tnb 94.84 7.705 104 Tnb Tnb 700 K (2) Tnb (corrected) = 0.4791 Tnb + 282.7 Tnb > 700 K Take the gi values of 21.98, 24.22, and 88.46 for the CH3 , CH2 , and primary-OH groups. (Answer: a) 370.35 K b) 363.14 K) 5.20 As shown in Problem 4.1, the hydrostatic pressure distribution in uids can be calculated from the equation dP = g (1) dz where the distance z is measured in the direction opposite to gravity. The highest point on the earths surface is the top of Mount Everest, located in the Himalayas on the border of Nepal and China. It is approximately 8900 m above sea level. Combine Eq. (1) with the Clausius-Clapeyron equation, Eq. (5.6-10), to estimate the boiling temperature of water at the top of Mount Everest. The following data are provided: The average rate of decrease in air temperature with altitude is 6.5 K/ km, The air temperature at sea level is 293 K, The heat of vaporization of water is 40, 800 J/ mol and it may be considered independent of temperature, The molecular weight of air is 29 g/ mol. (Answer: 342.9 K) 5.21 Based on Eq. (5.6-12), it is possible to express the vapor pressure of substances as a function of temperature in the form
vap log Pr = a

b Tr

(1)

which is valid from the triple point to the critical point. For monatomic gases (Ar, Kr, Xe), vap vap Pitzer et al. (1955) plotted log Pr versus 1/Tr and noted that log Pr takes the value of 1 at Tr = 0.7 (or 1/Tr = 1.43).
vap a) Using the following data for n-pentane, plot log Pr versus 1/Tr .

T ( K) P vap ( bar)

298 0.6833

323 1.5923

348 3.2340

373 5.9447

398 9.9109

423 15.5454

448 23.0773

b) Using the method of least squares show that the data are represented by
vap log Pr = 2.883

2.894 Tr

(2)

124

c) Use Eq. (3.1-14) and calculate the acentric factor for n-pentane. 5.22 Under atmospheric pressure, the heat of fusion and the melting temperature of p-xylene are 17, 127 J/ mol and 286.4 K, respectively. Determine the entropy change on fusion. (Answer: 59.8 J/ mol. K) 5.23 The vapor pressure of n-heptanol is 84.398 kPa at 443.15 K and the normal boiling temperature is 448 K. Estimate the heat of vaporization of n-heptanol. (Answer: 62, 208 J/ mol) 5.24 The vapor pressure of methyl sulfoxide is correlated by Douglas (1948) as a function of temperature in the form log P vap = 26.5 3539.32 6 log T T 293.15 T 323.15

where P vap is in mmHg and T is in K. Estimate the heat of vaporization of methyl sulfoxide at 298.15 K. (Answer: 52.9 kJ/ mol) 5.25 Uracil (C4 H4 N2 O2 ) is an organic base of the pyrimidine family. The sublimation pressure of uracil as a function of temperature is given below (Brunetti et al., 2000) T ( K) 397.0 404.0 409.0 416.0 419.5 424.0 P ( Pa) 4.365 102 8.128 102 1.260 101 2.188 101 2.951 101 4.266 101 T ( K) 428.0 431.0 435.5 440.0 443.0 P ( Pa) 5.370 101 7.244 101 1.047 1.479 1.950

Calculate the heat of sublimation of uracil. (Answer: 119.2 kJ/ mol) 5.26 The following data are available for iodine liquid = 4000 kg/ m3
vap ln Pliquid = 47.83

solid = 4930 kg/ m3

vap ln Psolid = 34.16

where P vap

7381 5.18 ln T T is in atm and T is in K.

8240 2.51 ln T T

a) Calculate the values of temperature and pressure at the triple point and plot a representative phase diagram for iodine. b) When iodine vapor, initially at 0.06 atm and 430 K, is cooled at constant pressure, determine the temperature at which the condensed phase rst appears? What is this condensed phase? c) When iodine vapor, initially at 0.21 atm and 430 K, is cooled at constant pressure, determine the temperature at which the condensed phase rst appears? What is this condensed phase? d) Calculate the heat of fusion of iodine at the triple point. e) Calculate the normal boiling temperature of iodine. (Answer: a) 385.5 K, 0.115 atm b) 372.6 K c) 403 K d) 15, 700 J/ mol e) 459 K) 125

5.27 Using the following data provided for n-hexanol (C6 H14 O) Normal boiling temperature = 430 K Normal melting temperature = 226 K e H vap = 44.5 kJ/ mol e H f us = 15.48 kJ/ mol

estimate its vapor pressure at a) 200 K, b) 415 K. (Answer: a) 2.08 107 atm b) 0.638 atm) 5.28 The vapor pressure of phenol as a function of temperature is given by ln P vap = 11.04 ln T where P vap is in kPa and T is in K. a) Calculate the heat of vaporization at the triple point temperature of 314.06 K. b) If the heat of fusion is 11, 514 J/ mol, show that the sublimation pressure of phenol is expressed as 8181 ln P sub = 31.34 T where P sub is in Pa and T is in K. (Answer: a) 56, 501 J/ mol) 5.29 The sublimation pressure of solid benzene is 299 Pa at 243 K. The vapor pressure of liquid benzene is 6022 Pa at 283 K. If the triple point of benzene is at 278.5 K and 4786 Pa, estimate its heat of fusion. (Answer: 10.5 kJ/ mol) 5.30 One gram of copper is placed in a rigid tank having a volume of 1 m3 . Once the air is evacuated, the tank is sealed and the temperature is increased to 1600 K. The melting point of copper is 1356 K and the vapor pressure of liquid copper is given by ln P vap = 39, 129 + 14.203 T 10, 000 + 93.275 + 4.32 106 T 2 T

where P vap is in atm and T is in K. a) How many phases are present within the tank? b) Estimate the heat of vaporization of copper. (Answer: a) 2 (liquid and vapor) b) 325.3 kJ/ mol) 5.31 Using the Peng-Robinson equation of state, estimate the maximum amount of propane that can be stored as vapor in a 0.1 m3 tank at 250 K. (Answer: 0.5 kg) 5.32 What should be the minimum pressure inside the container of a disposable butane lighter at a temperature of 298 K? Assume that n-butane is represented by the Peng-Robinson equation of state. (Answer: 2.43 bar) 126

5.33 At what temperature does the pure methane liquefy under atmospheric conditions? Assume that methane is represented by the Peng-Robinson equation of state. (Answer: 111.55 K) 5.34 Propylene is to be transported through a pipeline as a liquid. If the maximum temperature expected in the summer is around 330 K, estimate the minimum pressure that should be imposed in the pipeline. Assume that propylene is represented by the Peng-Robinson equation of state. (Answer: 23.6 bar) 5.35 Determine the state of methanol, i.e., liquid or vapor, under the following conditions: a) T = 550 K and P = 2000 bar b) T = 550 K and P = 1 bar c) T = 350 K and P = 2 bar d) T = 350 K and P = 1 bar 5.36 A piston-cylinder assembly initially contains 4 moles of substance X in vapor phase at 0.8 bar and 373 K. The vapor is compressed isothermally and reversibly until the rst droplet of liquid forms. Calculate the heat and work interactions with the surroundings if the vapor obeys the virial equation of state with B = 1887 cm3 / mol. The normal boiling temperature and the heat of vaporization of substance X are 354.8 K and 29, 750 J/ mol, respectively. (Answer: Q = 9032 J W = 9032 J) 5.37 When common gas-liquid-solid transitions take place, while temperature remains constant during vaporization, condensation, and sublimation, volume and entropy show abrupt change. Such transformations are called "rst-order transitions". Noting that G G =V and = S P T T P the derivatives of Gibbs energy are discontinuous for a rst-order transition. Since H = G+T S, enthalpy is also discontinuous at the transition temperature. A "second-order transition", on the other hand, is dened as one in which the rst derivative of Gibbs energy is continuous but the second derivative is discontinuous at the transition temperature. In other words, quantities such as volume, entropy, and enthalpy remain unchanged during phase change. Transition of a paramagnetic material into a ferromagnetic one or vice versa is an example of a second-order transition. How does the heat capacity at constant pressure vary during the rst-order and second-order transitions? Problem related to Section 5.8 5.38 Lee and Edmister (1971) proposed the following empirical equation for predicting the fugacity of pure liquid hydrocarbons: A2 A6 f 2 6 2 3 2 = A1 + +A3 ln Tr +A4 Tr +A5 Tr + + A7 ln Tr + A8 Tr Pr +A9 Tr Pr ln Pr ln P Tr Tr Pr A11 3 2 + (1 Tr ) A10 + + A13 Tr Pr + A12 Tr Tr 127

where A1 A2 A3 A4 A5 = 6.32873 = 8.45167 = 6.90287 = 1.87895 = 0.33448 A6 = 0.018706 A7 = 0.286517 A8 = 0.18940 A9 = 0.002584 A10 = 8.7015 A11 = 11.201 A12 = 0.05044 A13 = 0.002255

Estimate the specic enthalpy of liquid n-pentane at 433 K and 18.5 bar relative to that of the ideal gas at the same temperature. (Answer: 264.5 J/ g)

128