c 2011 Ismail Tosun

Chapter 3 Calculation of Changes in Internal Energy, Enthalpy, and Entropy

In the previous chapter, general expressions for calculating changes in internal energy, enthalpy, and entropy are developed. These expressions contain partial derivatives involving temperature, pressure, and molar volume. The purpose of this chapter is to show how to evaluate these derivatives in a systematic manner. 3.1 EQUATIONS OF STATE Any mathematical relationship between temperature, pressure, and molar volume is called an equation of state, i.e., e) = 0 f (T, P, V (3.1-1) Equations of state can be expressed either in pressure-explicit form e) P = P (T, V (3.1-2) (3.1-3) or in volume-explicit form

Moreover, an equation of state can also be expressed in terms of the dimensionless compressibility factor, Z , as e PV Z= (3.1-4) RT 3.1.1 Ideal Gas Equation of State The ideal gas model is dependent on the following assumptions: Molecules occupy no volume, Collisions of the molecules are totally elastic, i.e., energy of the molecules before a collision is equal to the energy of the molecules after a collision. In other words, there are no interactions between the molecules. The equation of state for an ideal gas is given by e = RT PV (3.1-5)

e =V e (T, P ) V

Since Z = 1 for an ideal gas, the compressibility factor shows the deviation from ideal behavior. A representative plot of the compressibility factor as a function of pressure with temperature as a parameter is shown in Figure 3.1. 29

1.5

T1>T2>T3

T1 1.0 T2 T3 0.5 Ideal gas

Figure 3.1 Variation of Z as a function of P and T .

3.1.2 The Virial Equation of State The virial equation of state is useful for calculating thermodynamic properties in the gas phase. It can be derived from statistical mechanics and is given by an innite series in molar volume, e , as V e B (T ) C (T ) PV =1+ + ... (3.1-6) Z= + RT e e2 V V

The coecient, B (T ), is called the second virial coecient, C (T ) is called the third virial coecient, and so on. All virial coecients are dependent on temperature. In practice, terms above the third virial coecient are rarely used in chemical thermodynamics. An equivalent form of the virial expansion is an innite series in pressure expressed as Z = 1 + B 0 (T ) P + C 0 (T ) P 2 + ... The coecients B 0 and C 0 can be expressed in terms of B and C as B0 = B RT and C0 = C B2 (RT )2 (3.1-8) (3.1-7)

In practice, it is recommended to consider only the second virial coecient for pressures up to 15 bar. Under these circumstances, Eq. (3.1-7) takes the form Z =1+ BP RT (3.1-9)

Van Ness and Abbott (1982) proposed the following equation to estimate the second virial coecient for nonpolar uids: i RTc h (0) B + B (1) (3.1-10) B= Pc 30

where

B (0) = 0.083 B (1)

0.422 1.6 Tr 0.172 = 0.139 4.2 Tr P Pc

vap log Pr

(3.1-11) (3.1-12)

The terms Tr , reduced temperature, Pr , reduced pressure, and , acentric factor, are dened by Tr = T Tc and Pr = (3.1-13) (3.1-14)

vap = 1.0 log( Pr |Tr =0.7 )

The denition of the acentric factor is based on the observation that versus 1/Tr is vap = 1 approximately a straight line (Pitzer et al., 1955)1 . For noble gases (Ar, Kr, Xe) log Pr at 1/Tr = 1/0.7 ' 1.43, indicating that = 0. With reference to Figure 3.2, Pitzer (1977) explained the conceptual basis of the acentric factor as follows: "Intermolecular forces operate between the centers of regions of substantial electron density. These centers are the molecular centers for Ar and (approximately) for CH4 , but are best approximated by the separate CH3 and CH2 groups in C3 H8 - hence the name acentric factor for the forces arising from points other than molecular centers."

Figure 3.2 The conceptual basis of the acentric factor. Example 3.1 Calculate the molar volume of ethylene at 350 K and 10 bar if it obeys the virial equation of state. Solution From Appendix A Tc = 282.5 K
1

Pc = 50.6 bar

= 0.089

See Problem 5.21.

31

The reduced temperature and pressure values are 350 10 = 1.239 Pr = = 0.198 Tr = 282.5 50.6 The terms B (0) and B (1) are calculated from Eqs. (3.1-11) and (3.1-12) as 0.422 B (0) = 0.083 = 0.217 (1.239)1.6 0.172 = 0.069 B (1) = 0.139 (1.239)4.2 The use of Eq. (3.1-10) in Eq. (3.1-9) leads to i Pr h (0) Z =1+ B + B (1) Tr Substitution of numerical values into Eq. (1) results in i 0.198 h 0.217 + (0.089)(0.069) = 0.966 Z =1+ 1.239 Therefore, the molar volume is e = ZRT = (0.966)(83.14)(350) = 2811 cm3 / mol V P 10 3.1.3 Cubic Equations of State

(1)

e , T ), some The cubic equations of state are expressed in pressure-explicit form, i.e., P = P (V of which are given in Table 3.1. The cubic equations of state have been extensively used over the last three decades2 , Soave-Redlich-Kwong and Peng-Robinson3 being the most popular ones. The reason for this is twofold: (i) they are applicable over a wide range of pressures and temperatures, (ii) they are capable of describing substances in both liquid and vapor phases. Table 3.1 Cubic equations of state. Equation van der Waals P RT a e b V e2 V 27 64 a Pc ! 2 ! b 1 8 RTc Pc

R2 Tc

Redlich-Kwong

Soave-RedlichKwong

RT a e b V e (V e + b) T V RT a e b V e (V e + b) V

0.42748

2.5 R2 Tc

Pc
2 R2 Tc

0.08664

RTc Pc RTc Pc RTc Pc

0.42748

Pc
2 R2 Tc

! !

0.08664

Peng-Robinson
2 3

For a comprehensive review on the state of the cubic equations of state, see Valderrama (2003). Peng-Robinson equation of state is one of the most widely used correlations in chemical engineering. To celebrate the twentieth anniversary of its publication, a symposium was organized in Edmonton, Canada, in 1996. Papers presented at the symposium were published in a special issue of Industrial and Engineering Chemistry Research (May 1998).

RT a e b V e (V e + b) + b(V e b) V

0.45724

Pc

0.07780

32

These equations are called "cubic" because they are of the third degree in molar volume, i.e., e 3 + c1 V e 2 + c2 V e + c3 = 0 (3.1-15) V

A typical isotherm of a cubic equation of state is shown in Figure 3.3-a. The horizontal line joining the points L and V is drawn so that the areas N and M are equal, known as the Maxwell equal area rule. The points L and V represent the saturated liquid and saturated vapor, respectively, at the given temperature T . The intersection of the horizontal line on the pressure axis gives the vapor (or saturation) pressure5 of the substance at T . When this procedure is repeated for other isotherms as well, the resulting pressure versus specic volume diagram is shown in Figure 3.3-b. Vapor and liquid phases exist in equilibrium within the dome-shaped region. The critical isotherm is tangent and has a point of inection at the critical point. The resulting mathematical expressions, i.e., 2 P P = =0 (3.1-17) e Tc e 2 Tc V V are used to evaluate the parameters "a" and "b" appearing in the cubic equations of state given in Table 3.1.

e b), and accounts In each equation given in Table 3.1, the rst term is identical, i.e., RT /(V for the repulsive forces between the molecules. The second term, on the other hand, is dierent in each equation and accounts for the attractive forces between the molecules. The parameters "a" and "b" are representative of attractive forces and volume of a molecule, respectively4 . Note that the parameter "a" in the van der Waals and Redlich-Kwong equations of state is a constant. In the case of Soave-Redlich-Kwong and Peng-Robinson equations of state, however, it is dependent on temperature through the term dened by 2 Soave-Redlich-Kwong 1 + 0.480 + 1.574 0.176 2 1 Tr (3.1-16) = 2 2 1 + 0.37464 + 1.54226 0.26992 1 Tr Peng-Robinson

P P Critical Point

vap

L N

V Tc T1

T VAPOR-LIQUID REGION T2

L V (a)

V V

V (b)

Figure 3.3

Pressure versus specic volume diagram for a pure substance.

At a given temperature and pressure, the solution of Eq. (3.1-15) gives three roots. When T > Tc , the only meaningful root is the one greater than b, the other two being complex
4 5

e must be greater than b. Why? The value of V Vapor pressure can be thought of a measure of the escaping tendency of a pure substance.

33

conjugate numbers. On the other hand, when T < Tc , depending on the value of pressure we can conclude the following: (i) P = P vap , the liquid and vapor phases are in equilibrium, the largest and the smallest roots correspond to the molar volumes of the saturated vapor and liquid phases, respectively; the intermediate root has no physical meaning, (ii) P < P vap , the uid is superheated vapor and the largest root gives its molar volume, (iii) P > P vap , the uid is compressed liquid and the smallest root gives its molar volume. It is also possible to express Eq. (3.1-15) in terms of the compressibility factor Z as Z3 + p Z2 + q Z + r = 0 (3.1-18)

where the coecients p, q, and r are given in Table 3.2. Since the value of Z generally lies between 0 and 1, Eq. (3.1-18) is preferred over Eq. (3.1-15). Table 3.2 Parameters in Eq. (3.1-18)6 . Eq. of State VDW A ! 27 Pr 2 64 Tr 0.42748 Pr
2.5 Tr

B 1 8 ! Pr Tr Pr Tr Pr Tr Pr Tr

p 1 B

q A

r AB

RK

0.08664

A B B2 A B B2 A 2B 3B 2

AB

SRK

0.42748

Pr
2 Tr

! !

0.08664

AB AB + B 2 + B 3

PR

0.45724

Pr
2 Tr

0.07780

1 + B

In engineering calculations, it is always more convenient to work with dimensionless quantities. For this reason, in Table 3.2, the parameters a and b are expressed in terms of the dimensionless parameters A and B dened by aP (RT )2 van der Waals, Soave-Redlich-Kwong, Peng-Robinson (3.1-19) Redlich-Kwong bP RT

A=

aP R2 T 2.5

B=

(3.1-20)

Example 3.2 Estimate the molar volume of methane at 340 K and 30 bar using the PengRobinson equation of state.
6

VDW - van der Waals, RK - Redlich-Kwong, SRK - Soave-Redlich-Kwong, PR - Peng-Robinson

34

Solution An algorithm to obtain the molar volume is as follows: 1. 2. 3. 4. 5. 6. 7. Obtain Tc , Pc , and from Appendix A, Calculate reduced temperature and reduced pressure, Use Eq. (3.1-16) to determine the term , 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, e = ZRT /P and determine the molar volume. Use V Tc = 190.6 K Pc = 46.1 bar = 0.011

From Appendix A

The reduced temperature is Tr = The reduced pressure is Pr = P 30 = 0.651 = Pc 46.1 T 340 = 1.784 = Tc 190.6

The use Eq. (3.1-16) gives the term as n h i o2 = 1 + 0.37464 + (1.54226)(0.011) (0.26992)(0.011)2 1 1.784 = 0.754

The dimensionless parameters A and B are calculated as ! Pr (0.45724)(0.651)(0.754) A = 0.45724 = 0.071 = 2 (1.784)2 Tr Pr (0.07780)(0.651) = 0.028 B = 0.07780 = Tr 1.784 The parameters p, q , and r are calculated as p = 1 + B = 1 + 0.028 = 0.972

r = AB + B 2 + B 3 = (0.071)(0.028) + (0.028)2 + (0.028)3 = 1.182 103 Equation (3.1-18) takes the form Z 3 0.972 Z 2 + 0.011 Z 1.182 103 = 0 Therefore, the molar volume is given by e = ZRT = (0.962)(83.14)(340) = 906.4 cm3 / mol V P 30 Example 3.3 A 1 m3 rigid tank contains 25 kg of propylene at 298 K. Determine the pressure and the state of propylene in the tank using the Peng-Robinson equation of state. The vapor pressure of propylene at 298 K is 11.53 bar. 35 Z = 0.962

q = A 2 B 3 B 2 = 0.071 (2)(0.028) (3)(0.028)2 = 0.011

Solution From Appendix A Tc = 365.2 K Pc = 46.0 bar = 0.144 M = 42.08 g/ mol

The state of a single-phase, single-component system can be specied by two independent intensive properties. The state of propylene lies on the 298 K isotherm as shown in the gure below. To identify the exact location, one more independent intensive property must be known besides temperature.
P

Pvap

T = 298 K

%L V

%V V

% V

Since the tank volume and the amount of propylene are given, this additional intensive property is the molar volume, calculated as e= V 1 = 1.683 m3 / kmol 25 42.08

To determine the state of propylene, this value must be compared with the molar volumes of e V at 298 K and 11.53 bar, it is rst e L and V saturated liquid and vapor. To determine V L V necessary to calculate Z and Z . The reduced temperature and pressure values are Tr = T 298 = 0.816 = Tc 365.2 and Pr = P 11.53 = 0.251 = Pc 46

The dimensionless parameters A and B are calculated as ! Pr (0.45724)(0.251)(1.118) A = 0.45724 = 0.193 = 2 (0.816)2 Tr Pr (0.07780)(0.251) = 0.024 = B = 0.07780 Tr 0.816 Z 3 0.976 Z 2 + 0.143 Z 4.042 103 = 0 The solution gives Z L = 0.037 and Z V = 0.804 Therefore, molar volumes of the saturated liquid and vapor are

The use Eq. (3.1-16) gives the term as n h i o2 = 1 + 0.37464 + (1.54226)(0.144) (0.26992)(0.144)2 1 0.816 = 1.118

The cubic equation in terms of the compressibility factor, Eq. (3.1-18), takes the form

L 2 e L = Z RT = (0.037)(8.314 10 )(298) = 0.080 m3 / kmol V P 11.53

36

V 2 e V = Z RT = (0.804)(8.314 10 )(298) = 1.728 m3 / kmol V P 11.53 L V e <V e <V e , propylene exists as a two-phase mixture and the pressure within the tank Since V is 11.53 bar. The mole fraction of vapor in the tank, x, is given by

x=

3.2 CALCULATION OF THE CHANGE IN INTERNAL ENERGY In the previous chapter, the general equation to calculate the change in internal energy was given by Eq. (2.2-26), i.e., P e e e dU = CV dT + T P dV (3.2-1) T V e

e V eL 1.683 0.080 V = 0.97 = 1.728 0.080 eL eV V V

This equation is valid for gases, liquids, and solids.

3.2.1 Change in Internal Energy for Liquids and Solids For solids and liquids, it is more convenient to express Eq. (3.2-1) in terms of the coecient of thermal expansion, , and isothermal compressibility, . As shown in Example 2.1, the use of the triple product rule leads to P (3.2-2) = T V e (3.2-3)

eV ' C eP give7 Substitution of Eq. (3.2-2) into Eq. (3.2-1) and using C T e e e P dV dU = CP dT +

3.2.2 Change in Internal Energy for Gases

The use of Eq. (2.2-54) in Eq. (3.2-4) results in ! e U e (P T ) =V P

T

The variation of internal energy with pressure at constant temperature is ! e ! e V T U P = P P

T T

(3.2-4)

(3.2-5)

The term (P/T )V e in Eq. (3.2-1) can be evaluated once the equation of state is known. It should be noted, however, that the heat capacity data are available only at ideal gas conditions, e . Therefore, it is necessary to develop an equation relating the i.e., as either P 0 or V e . Since U e is a state function, i.e., exact dierential, the e actual value of CV to an ideal one, C V use of Eq. (1.2-2) in Eq. (3.2-1) leads to ! eV C P T = P (3.2-6) T T V e e e V V T
7

eV ' C eP if T 2 /(C bP ) 1. As shown in Problem 2.3, C

37

Under isothermal conditions, integration of Eq. (3.2-7) from ideal gas state to real gas state gives Z real gas Z real gas 2 P eV = T e dC dV (3.2-8) T 2 V e ideal gas ideal gas or Z V e 2 P eV = C e +T e T = constant C dV (3.2-9) V 2 e T V

Carrying out the dierentiation leads to ! 2 eV P C =T T 2 V e e V

T

(3.2-7)

Appendix B gives the molar heat capacities of gases in the ideal gas state as a function of temperature in the form eP = a + bT + cT2 + dT3 + eT4 (3.2-11) C e can be found from the relationship The value of C V
eV eP C =C R

Substitution of Eq. (3.2-9) into Eq. (3.2-1) gives the change in internal energy as # " Z V e 2 P P e dT + T e e= C eV + T dV P dV (3.2-10) dU T 2 V T V e e

(3.2-12)

e1 , T1 ) to a nal Let us consider a process in which the system goes from an initial state (V e is independent of e2 , T2 ). Since internal energy is a state function, calculation of U state (V the path chosen in going from state 1 to state 2. The most convenient paths to be followed for the integration of Eq. (3.2-10) in going from state 1 to state 2 are shown in Figure 3.4.
~ V ~ V2 ~ V1 Path A

Path B

T1

T2

Figure 3.4

Paths of integration to calculate the change in internal energy.

Thus, the change in internal energy is given by e= U e= U Z Z Z P e P dV + T T V e1 e V T1

e2 V T2 T1 T2 T1

"

"

e + T C V

e1 V

2P T 2

e V

e dV

e + T C V Z

e2 V

2P T 2

dT +

e2 V P e T P dV T e e V1 V T2

e V

e dV

dT

Path A (3.2-13) Path B (3.2-14)

38

The use of Eqs. (3.2-13) and (3.2-14) requires the value of ( 2 P/T 2 )V e to be evaluated. Unless the equation of state is very simple, evaluation of this term may lead to a mathematically dicult expression to integrate. Such a diculty can be avoided by choosing an alternative e = indicates the ideal path for the integration of Eq. (3.2-1) as shown in Figure 3.5, where V gas state.
~ V ~ V =

~ V2 ~ V1

T1

T2

Figure 3.5

Alternative path of integration to calculate the change in internal energy.

The evaluation of Eq. (3.2-1) along the path shown in Figure 3.3 gives e= U Z

Depending on the equation of state, equations for calculating the change in internal energy are given below. van der Waals equation of state The use of the van der Waals equation of state in Eq. (3.2-15) leads to e =R U A1 T1 A2 T2 Z1 Z2 + Z
T2 T1

e1 V

P T

e V

T1

e+ dV

T2 T1

e dT + C V

e2 V

P e T P dV T V e T2

(3.2-15)

where the dimensionless parameter A is given in Table 3.2. Redlich-Kwong equation of state

e dT C V

(3.2-16)

The use of the Redlich-Kwong equation of state in Eq. (3.2-15) leads to e= U Z T2 3R A1 T1 B1 B2 A2 T2 e dT ln 1 + ln 1 + + C V 2 B1 Z1 B2 Z2 T1 (3.2-17)

where the dimensionless parameters A and B are given in Table 3.2. Peng-Robinson equation of state

The use of the Peng-Robinson equation of state in Eq. (3.2-15) leads to " # " # T2 (da/dT )T2 a2 Z + 1 + 2 B2 2 e= U ln 8b Z2 + 1 2 B2 " # " # Z T T1 (da/dT )T1 a1 2 Z1 + 1 + 2 B1 eV dT C ln + 8b Z1 + 1 2 B1 T1 39

(3.2-18)

where

da a = dT T = 0.37464 + 1.54226 0.26992 2 r Tr

(3.2-19)

in which

(3.2-20)

Substitution of Eq. (3.2-19) into Eq. (3.2-18) and rearrangement give " " # # Z Z + 1 + 2 B + 1 + 2 B2 A (1 + ) A (1 + ) RT RT 1 1 2 1 1 1 2 2 2 e= U ln ln 8 B1 Z1 + 1 2 B1 8 B2 Z2 + 1 2 B2 + Z
T2 T1

where the dimensionless parameters A and B are given in Table 3.2. Example 3.4 Show that Eqs. (3.2-14) and (3.2-15) are equivalent to each other. Solution Equation (3.2-14) is given as e= U Z
T2 eV dT + C

e dT C V

(3.2-21)

T1

Z |

T2

T1

" Z T

e1 V

Let us consider the term X in Eq. (1), i.e., Z "Z e

T2

2P T 2 {z
X

e V

e dV

dT + }

e1 V

e2 V

P e T P dV T V e T2

(1)

V1

X=

T1

2P T 2

Note that T

2P T 2

Changing the order of integration leads to Z

e1 V

Substitution of Eq. (3) into Eq. (2) gives ) Z T2 (Z V e1 P e dT T X= P dV T V e T1 T P e T X= P dT dV T V e T1 T Z V Z V e1 e1 P P e e T T = P dV P dV T V T e e V T2 T1 Z

T2

e V

P T P T T V e e V

e V

e dV

dT

(2)

(3)

(4)

(5)

40

Substitution of Eq. (5) into Eq. (1) gives e= U or e= U Z

T2 eV dT + C

T1

e1 V

T2

Z V e1 P P e e T T P dV P dV T V T e e V T2 T1 Z V e2 P e + P dV T T V e1 e V T2 Z
e2 V

T1

which is identical with Eq. (3.2-15).

eV dT + C

Z V e1 P P e e P dV P dV T T T V T V e e T2 T1

Example 3.5 Two moles of acetylene is compressed isothermally but irreversibly in a pistoncylinder assembly from 0.03 m3 and 350 K to 0.002 m3 . Calculate the work required if the heat removed from the system is 1.8 kJ. Acetylene is represented by the van der Waals equation of state. Solution From Appendix A Tc = 308.3 K Pc = 61.4 bar System: Acetylene within the piston-cylinder assembly Application of the rst law gives W = U Q Since the process is isothermal, i.e., T1 = T2 = T , Eq. (3.2-16) reduces to A1 A2 e U = RT Z1 Z2 The total change in internal energy is e = nRT U = n U A1 = Eq. (3) becomes U = n
2

(1)

(2)

A1 A2 Z1 Z2 P1 V1 nRT

Z2 = P2 V2 nRT

(3)

Noting that 27 Pr1 2 64 Tr

A2 =

27 Pr2 2 64 Tr
2 2 27 R Tc 64 Pc

Z1 = !

(4)

1 1 V1 V2

(5)

Substitution of the numerical values into Eq. (5) gives 5 2 2 1 1 2 27 (8.314 10 ) (308.3) = 8.427103 bar. m3 = 842.7 J U = (2) 64 61.4 0.03 0.002 The work done on the system can now be calculated from Eq. (1) as W = 842.7 + 1800 = 957.3 J

41

Example 3.6 A well-insulated rigid tank is divided into two equal parts of 3 104 m3 each by a rigid partition. One side contains 10 moles of methane at 500 K, and the other side is evacuated. The partition is removed and methane lls the entire tank. Using the van der Waals equation of state, determine the nal temperature of the gas. Solution From Appendix A Tc = 190.6 K From Appendix B
eP = 36.155 0.511 101 T + 2.215 104 T 2 1.824 107 T 3 + 4.899 1011 T 4 C

Pc = 46.1 bar

System: Contents of the tank

Application of the rst law gives W U = Q + |{z} |{z}

0 0

where subscripts 1 and 2 represent the initial and nal states, respectively. n1 = n2 = n and making use of the substitution A1 = 27 Pr1 2 64 Tr 1 A2 = 27 Pr2 2 64 Tr 2 Z1 = P1 V1 nRT1 Z2 = P2 V2 nRT2

If methane were an ideal gas, the temperature would remain constant at 500 K. In this case, however, methane is represented by the van der Waals equation of state and the change in internal energy is given by Eq. (3.2-16), i.e., Z T2 A1 T1 A2 T2 eV e + C dT = 0 (2) U = R Z1 Z2 T1 Noting that

e =0 U

(1)

(3)

Eq. (2) takes the form n

2 2 27 R Tc 64 Pc

1 1 V1 V2

T2

T1

The heat capacity at constant volume is

eP eV =C R C

eV dT = 0 C

(4)

= 27.841 0.511 101 T + 2.215 104 T 2 1.824 107 T 3 + 4.899 1011 T 4

Substitution of the numerical values into Eq. (4) gives 1 J 1 1 27 (8.314 105 )2 (190.6)2 (10) 64 46.1 3 104 6 104 105 bar. m3 Z T2 27.841 0.511 101 T + 2.215 104 T 2 1.824 107 T 3 + 4.899 1011 T 4 dT = 0 +
500

The solution of the above equation by MATHCAD

gives T2 = 390 K.

42

Example 3.7 Suppose that the methane in Example 3.6 is replaced by gas A, which is represented by the following equation of state: P = where a = 35 J. K. m3 / mol2 RT a e2 e b TV V and

Solution

e = 1.5 R, determine the nal temperature. If the ideal gas heat capacity of gas A is C V e =0 U Z
T2 T1

b = 4.8 105 m3 / mol

The change in internal energy is given by Eq. (3.2-15), i.e. e= U Z

e and W f are zero, then Since both Q P T

(1)

The integrand in Eq. (2) is evaluated using the given equation of state as P R P 2a a = T P = + T V T 2 2 e2 e e e e V T V TV V b Substitution of Eqs. (1) and (3) into Eq. (2) gives 2a 0= T1 Z
e1 V

e1 V

e V

T1

e+ dV

eV dT + C

e2 V

P e P dV T T V e T2

(2)

(3)

Carrying out the integration leads to

1 e dV + e2 V

T2

T1

2a 1.5 R dT + T2

e2 V

1 e dV e2 V

(4)

Substitution of the numerical values into Eq. (5) results in

2a 2a + 1.5 R(T2 T1 ) =0 e e T1 V T2 V 1 2

(5)

(2)(35) (2)(35) + (1.5)(8.314)(T2 500) =0 4 (500)(3 10 /10) T2 (6 104 /10) The solution of Eq. (6) gives T2 = 375.2 K.

(6)

Substitution of Eqs. (1), (3), and (7) into Eq. (3.2-13) leads to ! Z T2 Z e Z e 2 a V2 1 e 2 a V2 1 e 0= dV + dV dT 1.5 R 2 T1 V T V e1 V e2 e2 T1 43

Alternate solution: The solution is also possible by using either Eq. (3.2-13) or Eq. (3.2-14). Note that 2 2a P = (7) T 2 V e2 e T3 V (8)

or 2a 0= T1

Once the integration is carried out, the result is equivalent to Eq. (5). On the other hand, substitution of Eqs. (1), (3), and (7) into Eq. (3.2-14) leads to ! Z e Z e Z T2 2 a V2 1 e 2 a V1 1 e dV dT + dV 1.5 R 2 0= T T2 V e1 V e2 e2 T1 V or 0= Z
T2 T1

e1 V

e2 V

1 e dV + e2 V

T2

T1

2a 1.5 R + e T 2V

dT

(9)

(10)

Integration of Eq. (11) is also equivalent to Eq. (5).

2a 1.5 R + e T 2V

dT +

2a T2

e1 V

e2 V

1 e dV e V2

(11)

Example 3.8 A piston-cylinder assembly contains carbon monoxide at 283 K and 1 bar. It is compressed to a pressure of 80 bar by a reversible and isothermal process. Calculate the work and heat interactions with the surroundings if carbon monoxide obeys the following equation of state: e B PV C =1+ + RT e e2 V V with B = 23.1 cm3 / mol and C = 1560 cm6 / mol2 Solution System: CO within the piston-cylinder assembly The reversible work done in compressing the gas is given by f= W Z
e2 V

f is determined, the heat interaction is calculated indirectly from the rst law as Once W Substitution of the given equation of state into Eq. (1) gives f = RT W 1 C B e dV + + 2 3 e e e e V " 1 V! V V ! !# e2 1 V 1 1 1 C = RT ln B 2 V e e e e2 e2 V V V V 1 2 1 2 1 Z
e2 V

e1 V

e P dV

(1)

e = U eW f Q

(2)

(3)

Using MATHCAD , the initial and nal molar volumes are calculated from the equation of state as e1 23.1 (1) V 1560 e1 = 23, 506 cm3 / mol =1 + V (83.14)(283) 2 e e V V 1 1 44

Substitution of the numerical values into Eq. (3) results in 1 1 275 1 1560 1 f + 23.1 W = (8.314)(283) ln 23, 506 275 23, 506 2 (275)2 (23, 506)2 = 10, 295 J/ mol Since the process is isothermal Eq. (3.2-13) reduces to e= U Z
e2 V

e2 23.1 (80) V 1560 =1 + (83.14)(283) e e2 V V 2 2

e2 = 275 cm3 / mol V

From the given equation of state R P B C = 1+ + T V e e e2 e V V V

e1 V

P e P dV T T V e T1 T P T P =0

(4)

(5)

e = 0 and the heat interaction of the system with its surroundings can be calculated Therefore, U from Eq. (2) as e = 10, 295 J/ mol Q Example 3.9 Solve Example 3.5 if acetylene obeys the Peng-Robinson equation of state. Solution From Appendix A Tc = 308.3 K Pc = 61.4 bar = 0.190 The change in internal energy is calculated from Eq. (3.2-21). Since the process is isothermal, i.e., T1 = T2 = T = 350 K and 1 = 2 = , it simplies to " " ( # #) Z Z + 1 + 2 B + 1 + 2 B2 A RT (1 + ) A 1 1 2 1 2 e= U ln ln (1) B1 B2 8 Z1 + 1 2 B1 Z2 + 1 2 B2 Tr = T 350 = 1.135 = Tc 308.3

e V

The reduced temperature is

and the parameter is calculated from Eq. (3.1-16) as h i2 = 1 + 0.37464 + (1.54226)(0.190) (0.26992)(0.190)2 1 1.135 = 0.916 R2 Tc2 Pc = bar. m6 (0.45724)(8.314 105 )2 (308.3)2 (0.916) = 4.482 106 61.4 mol2

Therefore,

a = 0.45724

b = 0.07780

RTc (0.0778)(8.314 105 )(308.3) = 3.249 105 m3 / mol = Pc 61.4 45

The use of Eq. (3.2-20) gives 1 = 2 = 0.37464 + (1.54226)(0.190) (0.26992)(0.190)2 r 1.135 = 0.732 0.916

e1 = 0.03/2 = 0.015 m3 / mol) State 1 (T1 = 350 K, V P1 = (8.314 105 )(350) 0.015 3.249 105

The pressure is calculated from the Peng-Robinson equation of state as

4.482 106 = 1.924 bar (0.015)(0.015 + 3.249 105 ) + (3.249 105 )(0.015 3.249 105 ) Pr1 =

The reduced pressure is 1.924 = 0.031 61.4 The dimensionless parameters are calculated as ! Pr1 (0.45724)(0.031)(0.916) = 0.010 A1 = 0.45724 = 2 (1.135)2 Tr B1 = 0.07780 Pr1 Tr = (0.07780) (0.031) = 0.002 1.135

The cubic equation for Z , Eq. (3.1-18), takes the form

3 2 0.998 Z1 + 5.988 103 Z1 1.599 105 = 0 Z1

Z1 = 0.992

e2 = 0.002/2 = 0.001 m3 / mol) State 2 (T2 = 350 K, V The pressure is P2 = (8.314 105 )(350) 0.001 3.249 105

4.482 106 = 25.863 bar (0.001)(1 103 + 3.249 105 ) + (3.249 105 )(0.001 3.249 105 ) 25.863 = 0.421 61.4

Therefore, the reduced pressure is Pr2 =

The dimensionless parameters are calculated as ! Pr2 (0.45724)(0.421)(0.916) = 0.137 = A2 = 0.45724 2 (1.135)2 Tr B2 = 0.07780 Pr2 Tr = (0.07780) (0.421) = 0.029 1.135

The cubic equation for Z , Eq. (3.1-18), takes the form

3 2 0.971 Z2 + 0.076 Z2 3.108 103 = 0 Z2

Z2 = 0.889

46

Substitution of the numerical values into Eq. (1) gives + 0.732) e = (8.314)(350)(1 U 8 ( " # 0.992 + (1 + 2)(0.002) 0.010 ln 0.002 0.992 + (1 2)(0.002) " #) 0.889 + (1 + 2)(0.029) 0.137 ln = 702 J/ mol 0.029 0.889 + (1 2)(0.029)

Therefore, the work interaction is W = U Q = (2)( 702) + 1800 = 396 J which is quite dierent from the one calculated in Example 3.5. Comment: The results are strongly dependent on the equation of state used in the calculations.

3.3 CALCULATION OF THE CHANGE IN ENTHALPY In the previous chapter, the general equation to calculate the change in enthalpy was given by Eq. (2.2-31), i.e., " ! # e V e =C eP dT + V e T dH (3.3-1) dP T
P

This equation is valid for gases, liquids, and solids.

3.3.1 Change in Enthalpy for Liquids and Solids For solids and liquids, it is more convenient to express Eq. (3.3-1) in terms of the coecient of thermal expansion, . The use of Eq. (2.2-52) in Eq. (3.3-1) leads to e =C eP dT + V e (1 T ) dP dH (3.3-2)

e = 40.47 cm3 / mol) at 293 K Example 3.10 One mole of methanol ( = 12.0 104 K1 , V is compressed isothermally from 1 bar to 500 bar. Calculate the change in enthalpy. Solution Integration of Eq. (3.3-2) at constant temperature gives e =V e (1 T ) P H (1)

e and with pressure are considered negligible. Substitution of the in which variations in V values into Eq. (1) results in h i e = (40.47 106 ) 1 (12.0 104 )(293) (500 1) 105 = 1309 J/ mol H

47

3.3.2 Change in Enthalpy for Gases e , Since the heat capacity data are available only at ideal gas conditions, i.e., as P 0 or V e e it is rst necessary to develop an equation relating actual CP value to an ideal one, CP . Since e is a state function, i.e., exact dierential, the use of Eq. (1.2-2) in Eq. (3.3-1) leads to H ( ! " ! #) eP e C e V = (3.3-3) V T P T T
T P P

Carrying out the dierentiation leads to ! ! e eP 2V C = T P T 2

T

(3.3-4)

or

Under isothermal conditions, integration of Eq. (3.3-4) from ideal gas state to real gas state gives Z real gas Z real gas 2 e ! V eP = T dC dP (3.3-5) T 2 ideal gas ideal gas
P

Substitution of Eq. (3.3-6) into Eq. (3.3-1) gives the change in enthalpy as # " " ! # Z P 2e ! e V V e T e= C eP T dP dT + V dH dP T 2 T 0
P P

e T eP = C C P

P 0

e 2V T 2

dP

T = constant

(3.3-6)

(3.3-7)

Let us consider a process in which the system goes from an initial state (P1 , T1 ) to a nal e is independent of the path state (P2 , T2 ). Since enthalpy is a state function, calculation of H chosen in going from state 1 to state 2. The most convenient paths to be followed for the integration of Eq. (3.3-7) in going from state 1 to state 2 are shown in Figure 3.6 as paths A and B.
P P2 Path A Path B

P1

T1

T2

Figure 3.6

Paths of integration to calculate the change in enthalpy.

Thus, the change in enthalpy is given by e= H Z

P2 P1

"

e T V

e V T

! #

dP +

P T1

T2 T1

"

e T C P

P2 0

e 2V T 2

dP

dT

Path A (3.3-8)

48

e= H

T2 T1

"

e T C P

P1 0

e 2V T 2

dP

dT +

P2 P1

"

e T V

e V T

! #

dP

Path B (3.3-9)

P T2

Example 3.11 Ammonia is to be compressed from 350 K and 1 bar to 400 K and 50 bar. If the work supplied to the compressor is 1500 J/ mol, calculate the heat that must be supplied per mole of ammonia passing through the compressor. The equation of state is given by e b) = RT P (V

where b = 3.73 105 m3 / mol. Solution From Appendix B

System: Compressor

eP = 34.236 0.221 101 T + 1.213 104 T 2 1.088 107 T 3 + 3.203 1011 T 4 C

For a steady-state ow system, the rst law gives e , it is rst necessary to evaluate the partial derivatives appearing in Eqs. To calculate H (3.3-8) and (3.3-9) ! ! ! e e e V 2V R V e T = =0 V =b (2) T P T 2 T
P P P

e = H e W fs Q

(1)

or

Substitution of Eq. (2) either into Eq. (3.3-8) or into Eq. (3.3-9) gives Z T2 e eP H = b (P2 P1 ) + dT C
T1

(3)

e = (3.73 105 ) (50 1) 105 H Z 400 + 34.236 0.221 101 T + 1.213 104 T 2 1.088 107 T 3 + 3.203 1011 T 4 dT
350

= 2078.2 J/ mol

The heat interaction is calculated from Eq. (1) as e = 2078.2 1500 = 578.2 J/ mol Q Example 3.12 An evacuated gas cylinder of 50 L volume is connected to a main line that supplies CO2 at the constant conditions of 400 K and 2 MPa. The valve between the line and the cylinder is opened and the cylinder quickly lls with CO 2 until the pressure is 2 MPa, and then the valve is closed. Calculate the temperature immediately after the valve is closed. The equation of state for CO2 is given by e b) = RT P (V 49

where b = 4.41 105 m3 / mol.

Solution From Appendix B

eP = 29.268 0.224 101 T + 2.653 104 T 2 4.153 107 T 3 + 20.057 1011 T 4 C

System: Contents of the cylinder

The unsteady-state material and energy balances become dnin dnout = dnsys | {z }
0 0 0 0

(1)

Note that Q is considered zero since lling takes place quickly and heat transfer is a slow process. Combination of Eqs. (1) and (2) leads to e )sys e in dnsys = d(nU H (3)

e in dnin H e dn + Q + W = d(nU e )sys H | out{z out } |{z} |{z}

(2)

e in is constant, integration of Eq. (3) gives Since H

The cylinder is initially evacuated, i.e., n1 = 0, and Eq. (4) simplies to e2 e in = U H (5)

e in (n2 n1 ) = n2 U e2 n1 U e1 H

(4)

e 2 P2 V e2 = H e2 , reduces Eq. (5) to Expressing internal energy in terms of enthalpy, i.e., U The use of the equation of state results in e2 H e in e2 = H P2 V

(6)

The right-hand side of Eq. (7) can be calculated from either Eq. (3.3-8) or Eq. (3.3-9). Both equations simplify to Z T2 e e eP dT (8) H2 (2 MPa, T2 ) Hin (2 MPa, 400 K) = C
400

e 2 (2 MPa, T2 ) H e in (2 MPa, 400 K) RT2 + bP2 = H

(7)

Substitution of Eq. (8) into Eq. (7) gives

RT2 + bP2 = or

T2

400

eP dT C

(9)

8.314 T2 + (4.41 105 )(2 106 ) = Z T2 (29.268 0.224 101 T + 2.653 104 T 2 4.153 107 T 3 + 20.057 1011 T 4 ) dT
400

(10)

50

Solution of Eq. (10) by MATHCAD

gives T2 = 498 K.

Comment: It is implicitly assumed that there is no heat transfer between the cylinder surface and CO2 . Under what conditions is this assumption valid?

Since equations of state are not explicit in molar volume, evaluation of the the cubic 2 2 e e terms V /T and V /T in Eqs. (3.3-8) and (3.3-9) causes diculty. The term P P e /T V can be evaluated by the use of the triple product rule as
P

e V T

For example, if a gas is represented by the Redlich-Kwong equation of state, i.e., RT a e b V e (V e + b) T V

e) (P/ V T

(P/T )V e

(3.3-10)

P = then e V T !

(3.3-11)

e /T 2 )P into Eqs. (3.3-8) and Substitution of Eq. (3.3-12) together with the term ( 2 V (3.3-9) leads to a formidable equation. To circumvent mathematical complexity, an alternative path is chosen for the integration of Eq. (3.3-1) as shown in Figure 3.7, where P = 0 indicates the ideal gas state.
P P2

e + b) a (2V e b)2 e + b)2 T e 2 (V (V V RT

R a + e e e V b 2 V (V + b) T 3/2

(3.3-12)

P1 0

T1

T2

Figure 3.7

Alternative path of integration to calculate the change in enthalpy.

The evaluation of Eq. (3.3-1) along the path shown in Figure 3.5 gives e= H Z |
0 P1

"

It is apparent that the use of Eq. (3.3-13) is much simpler than that of Eqs. (3.3-8) and (3.3-9). However, in the case of cubic equations of state, evaluation of the terms X and Y in 51

e e T V V T {z
X

! #

dP + }

P T1

T2 T1

e dT + C P

Z |

P2 0

"

e e T V V T {z
Y

! #

dP }

(3.3-13)

P T2

Eq. (3.3-13) is notstraightforward. While integrations in Eq. (3.3-13) are with respect to P , e as can be seen from Eq. (3.3-12). e /T leads to an expression containing V the term V P Therefore, it is useful to have an integration over volume rather than pressure. For this purpose consider the integral ! # Z P" e V e T dP (3.3-14) V T 0
P T

e ), then Since P = P (T, V

dP =

Substitution of Eq. (3.3-16) into Eq. (3.3-14) gives " ! # ! # Z P" Z V e e e P V V P e e T e dP = T dV V V T T e T e T 0 V V P T P T From the triple product rule e V T !
P

Note that the integrand in Eq. (3.3-14) is evaluated at constant temperature. Under the condition of constant temperature, Eq. (3.3-15) reduces to P e dV (3.3-16) dP = e V T (3.3-17)

P e V

e+ dV

P T

dT

(3.3-15)

e V

Thus, Eq. (3.3-13) takes the form e= H Z

The use of Eq. (3.3-18) in Eq. (3.3-17) leads to ! # Z P" Z V e e P P V e e e T dP = +T dV V V T T V e T e T 0 V

P T

P e V

P T

(3.3-18)

e V

(3.3-19)

e1 V

e V

e2 V

Depending on the equation of state, equations for calculating the change in enthalpy are given below. van der Waals equation of state The use of the van der Waals equation of state in Eq. (3.3-20) leads to Z T2 A A 2 1 e = RT2 Z2 1 e dT RT1 Z1 1 + H C P Z2 Z1 T1 52 (3.3-21)

P e e P +T dV V T V e T e T V 2

P e V

+T

P T

e T V 1

e+ dV

T2 T1

e dT C P

(3.3-20)

where the dimensionless parameter A is given in Table 3.2. Redlich-Kwong equation of state The use of the Redlich-Kwong equation of state in Eq. (3.3-20) leads to Z T2 3 A2 B2 3 A1 B1 e e dT H = RT2 Z2 1 ln 1 + ln 1 + C RT1 Z1 1 + P 2 B2 Z2 2 B1 Z1 T1 (3.3-22) where the dimensionless parameters A and B are given in Table 3.2. Peng-Robinson equation of state The use of the Peng-Robinson equation of state in Eq. (3.3-20) leads to " # " #) T2 (da/dT )T2 a2 Z + 1 + 2 B2 1 2 e = RT2 Z2 1 + H ln RT2 8b Z2 + 1 2 B2 ( " # " #) Z T T1 (da/dT )T1 a1 2 Z1 + 1 + 2 B1 1 eP RT1 Z1 1 + dT C + ln RT1 8b Z1 + 1 2 B1 T1 ( " #) Z2 + 1 + 2 B2 A2 (1 + 2 ) ln Z2 1 8 B2 Z2 + 1 2 B2 ( " (

(3.3-23)

where the derivative da/dT is given by Eq. (3.2-19). Substitution of Eq. (3.2-19) into Eq. (3.3-23) and expressing the resulting equation in dimensionless form yield e = RT2 H

RT1

The dimensionless parameters A and B are given in Table 3.2, and is dened by Eq. (3.2-20). Example 3.13 Propane gas is to be compressed irreversibly from 5 bar and 323 K to 15 bar and 343 K by an adiabatic compressor in a petrochemical plant. Calculate the work input per mole of propane passing through the compressor if a) Propane obeys the Redlich-Kwong equation of state, b) Propane obeys the Peng-Robinson equation of state. Solution From Appendix A Tc = 369.9 K From Appendix B
eP C = 29.595 + 0.838 101 T + 3.256 104 T 2 3.958 107 T 3 + 13.129 1011 T 4

#) Z T 2 Z1 + 1 + 2 B1 A1 (1 + 1 ) e dT ln C Z1 1 + P 8 B1 Z1 + 1 2 B1 T1

(3.3-24)

Pc = 42.5 bar

= 0.153

System: Compressor

53

This is a steady-state ow process and from the rst law fs e= Q e +W H |{z}

0

(1)

Therefore, the work input to the compressor is equal to the change in enthalpy. Determination of enthalpy at the compressor inlet (state 1) and outlet (state 2) requires reduced temperature and pressure values to be known: State 1 2 Tr 0.873 0.927 Pr 0.118 0.353

a) The enthalpy change is given by Eq. (3.3-22). Therefore, it is rst necessary to determine A, B , and Z values at the compressor inlet and outlet. State 1 [T1 = 323 K (P vap = 17.4 bar), P1 = 5 bar] The dimensionless parameters are calculated as ! Pr1 (0.42748)(0.118) = 0.071 = A1 = 0.42748 2.5 (0.873)2.5 Tr1 Pr1 (0.08664)(0.118) = 0.012 = B1 = 0.08664 Tr1 0.873 The cubic equation for Z , Eq. (3.1-18), takes the form
3 2 Z1 + 0.059 Z1 8.52 104 = 0 Z1

Z1 = 0.938

State 2 [T2 = 343 K (P vap = 25.8 bar), P2 = 15 bar] The dimensionless parameters are calculated as ! Pr2 (0.42748)(0.353) = 0.182 A2 = 0.42748 = 2.5 (0.927)2.5 Tr2 Pr2 (0.08664)(0.353) = 0.033 B2 = 0.08664 = Tr2 0.927 The cubic equation for Z , Eq. (3.1-18), takes the form
3 2 Z2 + 0.148 Z2 6 103 = 0 Z2

Z2 = 0.830

The third term on the right-hand side of Eq. (3.3-22) is calculated as Z 343 eP dT = 1612 J/ mol C
323

Thus, substitution of numerical values into Eq. (3.3-22) gives 0.033 3 0.182 e ln 1 + H = (8.314)(343) 0.830 1 2 0.033 0.830 3 0.071 0.012 (8.314)(323) 0.938 1 ln 1 + + 1612 = 676.9 J/ mol 2 0.012 0.938 54

b) The enthalpy change is given by Eq. (3.3-24). Therefore, it is rst necessary to determine A, B , , and Z values at the compressor inlet and outlet. State 1 [T1 = 323 K (P vap = 17.4 bar), P1 = 5 bar] The parameter is calculated from Eq. (3.1-16) as h i2 = 1.081 1 = 1 + 0.37464 + (1.54226)(0.153) (0.26992)(0.153)2 1 0.873 1 = 0.37464 + (1.54226)(0.153) (0.26992)(0.153) h
2

The use of Eq. (3.2-20) gives

The dimensionless parameters are calculated as ! Pr1 (0.45724)(0.118)(1.081) A1 = 0.45724 = 0.077 1 = 2 (0.873)2 Tr1 ! Pr1 (0.07780)(0.118) = 0.011 B1 = 0.07780 = 0.873 Tr
1

i r 0.873 1.081

= 0.543

The cubic equation for Z , Eq. (3.1-18), takes the form

3 2 Z1 0.989 Z1 + 0.055 Z1 7.247 104 = 0

Z1 = 0.931

State 2 [T2 = 343 K (P vap = 25.8 bar), P2 = 15 bar] The parameter is calculated from Eq. (3.1-16) as h i2 2 = 1 + 0.37464 + (1.54226)(0.153) (0.26992)(0.153)2 1 0.927 = 1.046 2 = 0.37464 + (1.54226)(0.153) (0.26992)(0.153) h
2

The use of Eq. (3.2-20) gives

The dimensionless parameters are calculated as ! Pr2 (0.45724)(0.353)(1.046) A2 = 0.45724 = 0.196 2 = 2 (0.927)2 Tr2 ! Pr2 (0.07780) (0.353) = 0.030 B2 = 0.07780 = 0.927 Tr
2

i r 0.927 1.046

= 0.569

The cubic equation for Z , Eq. (3.1-18), takes the form

3 2 0.97 Z2 + 0.133 Z2 4.953 103 = 0 Z2

Z2 = 0.814

Finally, substitution of the numerical values into Eq. (3.3-24) gives the change in enthalpy as e = 1570 + 524 + 1612 = 566 J/ mol H 55

3.4 CALCULATION OF THE CHANGE IN ENTROPY In the previous chapter, the general equations to calculate the change in entropy are given by Eqs. (2.2-38) and (2.2-41), i.e., e= dS e= dS eV C T eP C T dT + P T e V T e dV dP (3.4-1)

dT

e V

(3.4-2)

These equations are valid for gases, liquids, and solids. 3.4.1 Change in Entropy for Liquids and Solids In terms of the coecient of thermal expansion, , and isothermal compressibility, , Eqs. (3.4-1) and (3.4-2) take the form e= dS e= dS eV C T eP C T dT + e dV (3.4-3)

e dP dT V

(3.4-4)

Example 3.14 Determine the change in entropy when liquid water at 1 bar and 298 K is compressed to 1000 bar and 323 K. The following data for water are available: T ( K) 298 298 323 323 Solution Since entropy is a state function, the path of integration is arbitrary. Let us consider the integration path as shown in the gure below:
P (bar) 1000

P ( bar) 1 1000 1 1000

eP ( J/ mol. K) C 75.305 75.314

e ( cm3 / mol) V 18.071 18.012 18.234 18.174

( K1 ) 256 106 366 106 458 106 568 106

298

323

T (K)

Integration of Eq. (3.4-4) gives e= S Z

T2

T1

Z P2 eP C e dP dT V T P1 56

(1)

eP is a weak function of temperature, it is possible to take the arithmetic average of C eP , Since C eP i, in going from 298 K to 323 K at a constant pressure of 1 bar. Similarly, it is possible hC e in going from 1 bar to 1000 bar at a constant to take the arithmetic averages of and V temperature of 323 K. Thus, Eq. (1) reduces to T2 e i (P2 P1 ) e e h i hV (2) S = hCP i ln T1 The average values are eP i = hC 75.305 + 75.314 = 75.310 J/ mol. K 2 458 + 568 h i = 106 = 513 106 K1 2 e i = 18.234 + 18.174 = 18.204 cm3 / mol hV 2

Substitution of the numerical values into Eq. (2) leads to i h 323 e (513 106 )(18.204 106 ) (1000 1) 105 = 5.13 J/ mol. K S = (75.310) ln 298 3.4.2 Change in Entropy for Gases For gases, the change in entropy can be calculated from either Eq. (3.4-1) or Eq. (3.4-2) once eP values to C e and C e , it is necessary to eV and C the equation of state is known. To relate C V P use Eqs. (3.2-9) and (3.3-6), respectively. The result is e 2 e Z V C V P P e e e + dV dT + dV (3.4-5) dS = T T 2 V T V e e e= dS Z e C P T Z
P 0

e 2V T 2

Integration of Eq. (3.4-5) over the paths shown in Figure 3.2 leads to e= S e= S Z Z
e2 V

dP dT
e2 V

e V T

dP

(3.4-6)

e1 V

P T

e T1 V e1 V

e+ dV 2P T 2

T2 T1

e C V T

2P T 2

T2 T1

e C V T

On the other hand, integration of Eq. (3.4-6) over the paths shown in Figure 3.4 results in e= S Z
P2 P1

e V

e dT + dV e C P T

e V

e dT dV e dV

Path A

(3.4-7)

e1 V

e2 V

P T

Path B

(3.4-8)

e T2 V

"

e V T

! #

dP +

P T1

T2 T1

P2 0

e 2V T 2

dP dT

Path A

(3.4-9)

57

e= S

T2 T1

e C P T

P1 0

e 2V

T 2

dP dT

P2 P1

"

e V T

! #

dP

Path B

(3.4-10)

P T2

Example 3.15 A 0.7 m3 insulated, rigid tank contains ammonia at 350 K and 50 bar. A valve on the tank is opened, and the pressure inside quickly drops to 10 bar, at which point the valve is closed. Calculate the mass of ammonia vented to the atmosphere if the equation of state is given by e b) = RT P (V where b = 3.73 102 m3 / kmol. Solution From Appendix B
eP C = 34.236 0.221 101 T + 1.213 104 T 2 1.088 107 T 3 + 3.203 1011 T 4

The dierence between the initial and nal mass of ammonia gives the amount of ammonia vented to the atmosphere. For this purpose, it is rst necessary to determine the nal temperature in the tank. System: Ammonia remaining in the tank when the pressure reaches 10 bar This is a closed system and if we assume that the system undergoes a reversible and adiabatic expansion then e2 e=0 e1 = S S S

The entropy change can be calculated from either Eq. (3.4-9) or Eq. (3.4-10). From the given equation of state, i.e., e = RT + b V P the following partial derivatives are obtained: ! ! e e V R 2V = =0 and T P T 2
P P

Thus, Eqs. (3.4-9) and (3.4-10) both reduce to 0= Z

T2

T1

Substitution of the numerical values results in Z T2 34.236 0.221 101 T + 1.213 104 T 2 1.088 107 T 3 + 3.203 1011 T 4 dT T 350 10 (8.314) ln =0 50 The solution by MATHCAD gives T2 = 240.6 K. The initial and nal molar volumes are calculated from the equation of state as
2 e1 = (8.314 10 )(350) + 3.73 102 = 0.6193 m3 / kmol V 50 2 e2 = (8.314 10 )(240.6) + 3.73 102 = 2.0376 m3 / kmol V 10
R

e C P T

dT

P2

P1

R dP P

58

The initial and nal number of moles of ammonia in the tank are n1 = V 0.7 = 1.13 kmol = 0.6193 e V
1 2

Therefore, the mass of ammonia vented to the atmosphere, m, is m = (n1 n2 )M

V 0.7 = 0.34 kmol = n2 = 2 . 0376 e V

= (1.13 0.34)(17) = 13.43 kg

The second-order derivatives in Eqs. (3.4-7)-(3.4-10) may lead to mathematically complicated expressions to integrate. To eliminate such a problem, Eq. (3.4-1) can be integrated along the path shown in Figure 3.3. The result is e= S Z

On the other hand, integration of Eq. (3.4-2) along the path shown in Figure 3.5 gives e= S Z
0 P1

e1 V

P T

e T1 V

e+ dV

T2 T1

e C V T

dT +

e2 V

P T

e T2 V

e dV

(3.4-11)

"

e V T

! #

dP +

P T1

T2 T1

e C P T

dT

P2 0

"

e V T

! #

dP

(3.4-12)

P T2

Depending on the equation of state, equations for calculating the change in entropy are given below. van der Waals equation of state The use of the van der Waals equation of state in Eq. (3.4-11) leads to8 e = R ln S Z2 B2 Z1 B1 Z
T2 T1

e C P T

dT R ln

P2 P1

(3.4-13)

where the dimensionless parameter B is given in Table 3.2. Redlich-Kwong equation of state The use of the Redlich-Kwong equation of state in Eq. (3.4-11) leads to e = R ln S +
8

Z2 B2 Z1 B1
T2

R A2 A1 B2 B1 ln 1 + ln 1 + 2 B2 Z2 B1 Z1 P2 P1

T1

e C P T

(3.4-14)

dT R ln

See Problem 3.21.

59

where the dimensionless parameters A and B are given in Table 3.2. Peng-Robinson equation of state The use of the Peng-Robinson equation of state in Eq. (3.4-11) leads to " # (da/dT ) Z + 1 + 2 B2 T Z B 2 2 2 2 e = R ln ln S + Z1 B1 8b Z2 + 1 2 B2 " # Z T e (da/dT )T1 2 C Z1 + 1 + 2 B1 P2 P ln dT R ln (3.4-15) + T P 8b Z1 + 1 2 B1 1 T1 " " # RA2 2 Z2 + 1 + 2 B2 ln 8 B2 Z2 + 1 2 B2

where the derivative term da/dT is given by Eq. (3.2-19). Substitution of Eq. (3.2-19) into Eq. (3.4-15) and expressing the resulting equation in dimensionless form yield e = R ln S Z2 B2 Z1 B1

The dimensionless parameters A and B are given in Table 3.2, and is dened by Eq. (3.2-20). Depending on the problem statement, one can use the following identity in Eqs. (3.4-13), (3.4-14), and (3.4-16) Z T2 C Z T2 C e e e2 V P P V 2 dT R ln dT + R ln (3.4-17) = P1 T1 T T1 T e V1 Example 3.16 Three moles of isobutane at 40 bar and 450 K is contained in a piston-cylinder assembly. Calculate the work interaction with the surroundings using the Redlich-Kwong equation of state if a) Isobutane expands reversibly and isothermally to 10 bar, b) Isobutane expands reversibly and adiabatically to 10 bar. Solution From Appendix A Tc = 407.7 K From Appendix B
eP = 24.108 + 2.091 101 T + 2.166 104 T 2 3.372 107 T 3 + 11.619 1011 T 4 C

# Z T e 2 C RA1 1 Z1 + 1 + 2 B1 P2 P + dT R ln ln + P1 8 B1 Z1 + 1 2 B1 T1 T

(3.4-16)

Pc = 36.5 bar

= 0.183

System: Isobutane within the piston-cylinder assembly

a) The work done by isobutane during reversible expansion is calculated as Z V Z V e2 e2 a e = n e dV RT P dV W = n e1 e1 e V V V b e (V e + b) T V 60

(1)

In terms of the dimensionless parameters, A and B , dened in Table 3.2, Eq. (2) takes the form P2 Z1 B1 B1 B2 A1 A2 ln 1 + ln 1 + + ln + (3) W = nRT ln Z2 B2 P1 B1 Z1 B2 Z2 Note that the work interaction can also be calculated indirectly from the rst law as e Q e) W = n (U (4)

Since the process is isothermal, i.e., temperature remains constant at 450 K throughout the process, integration of Eq. (1) is straightforward, with the result " ! !# ! e1 b V b b a a W = n RT ln ln 1 + (2) + ln 1 + e b e e b T b T V V V
2 1 2

or

Substitution of Eqs. (3.2-17) and (3.4-14) into Eq. (5) also leads to Eq. (3). The reduced temperature and pressure are Tr1 = T1 450 = 1.104 = Tc 407.7 ! Pr1 = P1 40 = 1.096 = Pc 36.5 State 1 (T1 = 450 K, P1 = 40 bar)

e T S e) W = n (U

(5)

The dimensionless parameters are calculated as A1 = 0.42748 Pr1

2.5 Tr1

(0.42748)(1.096) = 0.366 (1.104)2.5 (0.08664)(1.096) = 0.086 1.104

B1 = 0.08664

Pr1 Tr1

The cubic equation for Z , Eq. (3.1-18), takes the form

3 2 Z1 Z1 + 0.273 Z1 0.031 = 0

Z1 = 0.656

State 2 (T2 = 450 K, P2 = 10 bar) The reduced temperature and pressure are Tr2 = T2 450 = 1.104 = Tc 407.7 Pr2 = P2 10 = 0.274 = Pc 36.5

The dimensionless parameters are calculated as ! Pr2 (0.42748)(0.274) = 0.091 A2 = 0.42748 = 2.5 (1.104)2.5 Tr2 Pr2 (0.08664)(0.274) = 0.022 B2 = 0.08664 = Tr2 1.104 61

The cubic equation for Z , Eq. (3.1-18), takes the form

3 2 Z2 + 0.069 Z2 2 103 = 0 Z2

Z2 = 0.928

Substitution of the numerical values into Eq. (3) gives 0.656 0.086 10 0.366 0.086 W = (3)(8.314)(450) ln + ln + ln 1 + 0.928 0.022 40 0.086 0.656 0.091 0.022 ln 1 + = 15, 964 J 0.022 0.928 b) Since temperature does not remain constant in this case, integration of Eq. (1) can only be possible numerically. Hence, it is much more convenient to calculate work indirectly from the rst law, i.e., (6) W = U Q |{z}
0

To calculate the change in internal energy, it is rst necessary to calculate the temperature at the nal state. Since the process is reversible and adiabatic (or isentropic), the entropy remains constant, i.e., e=0 S (7) or, from Eq. (3.4-14), R ln Z2 B2 Z1 B1 Z T2 e CP B2 B1 R A2 A1 dT ln 1 + ln 1 + + 2 B2 Z2 B1 Z1 T T1

R ln

P2 P1

= 0 (8)

The nal temperature T2 should be determined so as to satisfy Eq. (8). The results of the trial-and-error solution are given below: T2 ( K) 425 400 390 396 A2 0.106 0.123 0.131 0.126 B2 0.023 0.024 0.025 0.024 Z2 0.913 0.894 0.885 0.891 e ( J/ mol. K) S 9.282 1.312 1.926 0.020

Noting that

Thus, T2 ' 396 K and the change in internal energy is calculated from Eq. (3.2-17) as ( 3(8.314) (0.366)(450) 0.086 (0.126)(396) 0.024 ln 1 + ln 1 + U = (3) 2 0.086 0.656 0.024 0.891 Z 396 e + (9) CV dT
450

the work interaction is calculated from Eq. (9) as

396

450

eV dT = C

396

450

eP (C R) dT = 6544 J/ mol

W = U = 12, 873 J

62

3.5 THE LAW OF CORRESPONDING STATES According to the law (or principle) of corresponding states, the compressibility factor of uids is dependent only on the reduced temperature and pressure (or volume), i.e., Z = Z (Tr , Pr ) or er ) Z = Z (Tr , V (3.5-1)

In other words, uids must have the same compressibility factor at the same reduced temperature and pressure (or volume). This generalization comes from the fact that the van der Waals equation of state can be expressed in the form given by Eq. (3.5-1) as will be shown in the following example. Example 3.17 Show that the van der Waals equation of state can be expressed in the form given by Eq. (3.5-1). Solution The van der Waals equation of state is P = The use of Eq. (3.1-17) gives P =0 e Tc V Division of Eq. (2) by Eq. (3) yields b= 1e Vc 3 2P e2 V
Tc

a RT e b V e2 V RTc 2a = ec b)2 ec3 (V V

(1)

(2)

=0

RTc 3a = ec b)3 ec4 (V V

(3)

(4)

Substitution of Eq. (4) into Eq. (2) results in a=

The compressibility factor for the van der Waals equation of state is Z= e e V PV a = RT e b V e RT V er 1 V 3 er V 9 1 8V er Tr (6)

9 ec RTc V 8

(5)

Substitution of Eqs. (4) and (5) into Eq. (6) leads to Z=

(7)

er = Tr = 1. Thus, the critical compressibility factor, Zc , is Comment: At the critical point, V calculated from Eq. (7) as 3 Zc = = 0.375 8

63

The critical compressibility factor, Zc , is the value of Z at Pr = Tr = 1. If Eq. (3.5-1) were universally valid, all uids would have to have the same Zc value. In reality, however, Zc values for real uids range from 0.23 to 0.31. To make the principle of corresponding states applicable to all uids, Pitzer et al. (1955) introduced a third parameter and modied Eq. (3.5-1) as Z = Z (Pr , Tr , ) (3.5-2)

where is the acentric factor dened by Eq. (3.1-14). It takes into account the geometry (deviation from spherical shape) and polarity of a molecule. For simple uids, such as argon, krypton, and xenon, its value is zero. The functional form of Z is suggested in the form Z (Pr , Tr , ) = Z (0) (Pr , Tr ) + Z (1) (Pr , Tr ) (3.5-3)

Pitzer et al. (1955) tabulated the values of Z (0) and Z (1) as functions of Pr and Tr . These values were later improved by Lee and Kesler (1975) using the modied Benedict-Webb-Rubin equation of state as described in Appendix D. Example 3.18 Solve Example 3.1 if ethylene obeys the principle of corresponding states. Solution From Example 3.1 Tr = 1.239 Pr = 0.198 = 0.089 The use of Eq. (D-2) in Appendix D gives er(0) = 6.0522 V Z (0) = 0.9654 From Eq. (D-8) 0.9695 0.9654 = 0.0103 0.3978 The compressibility factor is calculated from Eq. (3.5-3) as Z (1) = Z = 0.9654 + (0.089)(0.0103) = 0.9663 e = 2811 cm3 / mol. which is almost the same as the Z value obtained in Example 3.1. Therefore, V 3.6 DEPARTURE FUNCTIONS Internal energy, enthalpy, and entropy are all state functions. When a system goes from an initial state of (T1 ,P1 ) to a nal state of (T2 ,P2 ), calculations of U , H , and S are independent of the path chosen. Such changes can be easily calculated if one chooses the path shown in Figure 3.8. For an ideal gas, the changes in enthalpy and entropy are given by Z T2 IG eP e dT (3.6-1) C H =
T1

and

The values of Z (0) and Z (R) are calculated from Eqs. (D-6) and (D-7), respectively, as and Z (R) = 0.9695

er(R) = 6.0776 V

64

(T1, P1 ) Ideal Gas

(T2 ,P2 )

Real Gas (T1, P1 ) (T2 ,P2 )

Figure 3.8

The path followed in the solution of thermodynamic problems. Z e C P T

Using the path shown in Figure 3.8, the changes in enthalpy and entropy are given by e = (H e H e IG )T ,P + H 1 1 e = (S eS eIG )T ,P + S 1 1 Z
T2 T1

eIG = S

T2

T1

dT R ln

P2 P1

(3.6-2)

T2 T1

e C P T

e H e IG )T ,P e dT + (H C 2 2 P P2 P1 eS eIG )T ,P + (S 2 2

(3.6-3)

dT R ln

(3.6-4)

The term departure function is dened as the change in property in going from the real state to the ideal gas state or vice versa at constant temperature and pressure, i.e., ( IG )T,P . In a similar fashion, the change in internal energy is given by e = (U e U e IG )T ,P + U 1 1 Z
T2 T1

e IG U e )T,P , is calculated indirectly from the The departure function for internal energy, (U departure function for enthalpy as follows. From the denition of enthalpy For an ideal gas, Eq. (3.6-6) reduces to e =U e + PV e =U e + ZRT H e IG + RT e IG = U H (3.6-6)

e U e IG )T ,P e dT + (U C 2 2 V

(3.6-5)

(3.6-7)

Subtraction of Eq. (3.6-7) from Eq. (3.6-6) gives

3.6.1 Departure Functions from the Cubic Equations of State Comparison of Eq. (3.6-3) with either Eq. (3.3-13) or Eq. (3.3-20) gives the departure function for enthalpy as e H e IG H = Z
P 0

e U e IG )T,P = (H e H e IG )T,P + (1 Z )RT (U

(3.6-8)

T,P

"

e T V

e V T

! #

dP =

P T

e V

P P e e +T dV V T e e V T V T (3.6-9)

65

On the other hand, comparison of Eq. (3.6-4) with Eq. (3.4-12) gives the departure function for entropy as ! # Z P" e V R eS eIG = dP (3.6-10) S P T T,P 0
P T

The use of Eqs. (3.3-16) and (3.3-18) in Eq. (3.6-10) also expresses the departure function for entropy in the form eS eIG S = Z
e V

T,P

P T

Departure functions for various equations of state are given below. van der Waals equation of state

e V

R e V

e + R ln Z dV

(3.6-11)

The use of the van der Waals equation of state in Eqs. (3.6-9) and (3.6-11) leads to e H e IG H RT IG e e SS R A Z

T,P

=Z 1

(3.6-12)

T,P

= ln (Z B )

(3.6-13)

where the dimensionless parameters A and B are given in Table 3.2. The use of Eq. (3.6-12) in Eq. (3.6-8) gives e U e IG U A T,P = (3.6-14) RT Z Redlich-Kwong equation of state The use of the Redlich-Kwong equation of state in Eqs. (3.6-9) and (3.6-11) leads to e H e IG H RT eS eIG S R
T,P

T,P

3 A B =Z 1 ln 1 + 2B Z

(3.6-15)

1 A B = ln (Z B ) ln 1 + 2B Z

(3.6-16)

where the dimensionless parameters A and B are given in Table 3.2. The use of Eq. (3.6-14) in Eq. (3.6-8) gives e U e IG U 3 A B T,P = ln 1 + (3.6-17) RT 2B Z Peng-Robinson equation of state The use of the Peng-Robinson equation of state in Eqs. (3.6-9) and (3.6-11) leads to 66

 e H e IG H RT

T,P

1 =Z 1+ RT

eS eIG S R

# " Z + 1+ 2 B T (da/dT ) a ln 8b Z + 1 2 B da/dT 8b # Z + 1+ 2 B ln Z + 1 2 B "

(3.6-18)

T,P

1 = ln(Z B ) + R

(3.6-19)

where the dimensionless parameters A and B are given in Table 3.2, and the derivative term da/dT is given by Eq. (3.2-19). Substitution of Eq. (3.6-18) into Eq. (3.6-8) gives # e U e IG " U Z + 1 + 2 B T ( da/dT ) a T,P = ln (3.6-20) RT 8 bRT Z+ 1 2 B Equations (3.6-18)-(3.6-20) can be further simplied with the help of Eq. (3.2-19). The resulting equations are given as " # e H e IG H Z + 1+ 2 B A (1 + ) T,P ln =Z 1 (3.6-21) RT 8B Z + 1 2 B eS eIG S R
T,P

e U e IG U RT

" # Z+ 1+ 2 B A ln = ln(Z B ) 8B Z+ 1 2 B " # Z+ 1+ 2 B A (1 + ) ln = 8B Z+ 1 2 B

(3.6-22)

T,P

(3.6-23)

where is dened by Eq. (3.2-20).

Example 3.19 Isopentane is to be compressed from 3 bar and 500 K to 20 bar in a reversible isothermal compressor. Determine the work required per mole of isopentane as well as the heat interaction of the compressor with the surroundings. Assume that isopentane obeys the Peng-Robinson equation of state. Solution From Appendix A Tc = 461.0 K System: Compressor The rst law for a steady-state ow system is given by e =Q e+W fs H (1) Pc = 33.8 bar = 0.227

The values of reduced temperature, reduced pressure, and at the compressor inlet (state 1) and outlet (state 2) are calculated as 67

For a reversible and isothermal process, the heat interaction can be calculated from the second law as e = T S e Q (2)

State 1 2

Tr 1.085 1.085

Pr 0.089 0.592

0.942 0.942

The values of A, B , and Z , and the departure functions at the compressor inlet and outlet are given in the following table: e H e IG H ( J/ mol) 359.2 2647 eS eIG S ( J/ mol. K) 0.496 3.787

State 1 2

P ( bar) 3 20

A 0.033 0.217

B 6.382 103 0.042

Z 0.973 0.812

0.763 0.763

The change in enthalpy is calculated from Eq. (3.6-3) as e = (H e H e IG )T ,P + (H e H e IG )T ,P = 359.2 2647 = 2287.8 J/ mol H 1 1 2 2

The change in entropy is calculated from Eq. (3.6-4) as P2 IG eS eIG )T ,P e e e + (S S = (S S )T1 ,P1 R ln 2 2 P1 20 3.787 = 19.064 J/ mol. K = 0.496 (8.314) ln 3 The use of Eq. (2) gives the heat interaction as e = (500) ( 19.064) = 9532 J/ mol Q

The work done can be calculated from Eq. (1) as

e Q e = 2287.8 + 9532 = 7244.2 J/ mol fs = H W Example 3.20 A piston-cylinder assembly initially contains 0.1 m3 of ethylene at 393 K and 35 bar. The pressure of the gas is increased to 205 bar by a reversible isothermal compression. Calculate the heat and work interactions with the surroundings by assuming a) Ethylene is an ideal gas, b) Ethylene obeys the Peng-Robinson equation of state. Solution From Appendix A Tc = 282.5 K Pc = 50.6 bar = 0.089 System: Ethylene in the piston-cylinder assembly a) Since the internal energy of an ideal gas depends only on temperature, U = 0 and the rst law simplies to Q = W (1) 68

The work done on the gas can be determined from Z V2 Z V2 V2 nRT P1 dV = nRT ln W = = nRT ln P dV = V V1 P2 V1 V1 The number of moles of ethylene is n= (35)(0.1) P1 V1 = 0.107 kmol = RT1 (8.314 102 )(393)

(2)

Substitution of the values into Eq. (2) gives W = (0.107)(8.314)(393) ln From Eq. (1), Q = 618 kJ. b) For a reversible isothermal process, the second law states that Q = T S (3) 35 205 = 618 kJ

Therefore, once Q and U are calculated, the work done on the gas is calculated from the rst law, i.e., W = U Q (4) Determination of internal energy and entropy values at the initial (state 1) and nal (state 2) states requires reduced temperature, reduced pressure, and values to be known: State 1 2 Tr 1.391 1.391 Pr 0.692 4.051 0.825 0.825

The values of A, B , Z , and , and the departure functions at the initial and nal states are given in the table below:

State 1 2

P ( bar) 35 205

A 0.135 0.790

B 0.039 0.227

Z 0.908 0.740

0.662 0.662

e U e IG U ( kJ/ kmol) 775 4611

eS eIG S ( kJ/ kmol. K) 1.953 10.222

The number of moles of ethylene is n= (35)(0.1) P1 V1 = 0.118 kmol = R T1 Z1 (8.314 102 )(393)(0.908) e U e IG )T,P e = (U e U e IG )T,P + (U U 1 2 = 775 4611 = 3836 kJ/ kmol 69

Since the process is isothermal, i.e., T1 = T2 = T , Eq. (3.6-5) gives

Thus, the total change in internal energy is e = (0.118)( 3836) = 452.6 kJ U = n U

The change in entropy is calculated from Eq. (3.6-4) as P2 IG e e e eS eIG )T ,P S = (S S )T1 ,P1 R ln + (S 2 2 P1 205 10.222 = 22.965 kJ/ kmol. K = 1.953 (8.314) ln 35 The amount of heat exchange is h i Q = T S = (393) (0.118)( 22.965) = 1065 kJ W = 452.6 + 1065 = 612.4 kJ

The work done on the gas can be calculated from Eq. (4) as

3.6.2 Departure Functions from the Principle of Corresponding States Departure functions for enthalpy and entropy are given as (0) (1) e H e IG e H e IG e H e IG H H H T,P T,P T,P = + (3.6-24) RTc RTc RTc (0) (1) eS eIG eS eIG eS eIG S S S T,P T,P T,P = + (3.6-25) R R R Appendix D gives the equations developed by Lee and Kesler (1975) to calculate the terms on the right-hand sides of Eqs. (3.6-24) and (3.6-25). Example 3.21 Solve Example 3.13 if propane obeys the principle of corresponding states. Solution Note that From Appendix A Tc = 369.9 K e fs = H W

(1) = 0.153

Pc = 42.5 bar

From the equations given in Appendix D, the enthalpy departures are tabulated below. Therefore, the use of Eq. (3.6-24) gives e H e IG H T1 ,P1 = 0.159 + (0.153)( 0.194) = 0.189 RTc e H e IG H T2 ,P2 = 471 + (0.153)( 527) = 0.552 RTc 70

Parameters e (0) V r
(0)

State 1 (Tr = 0.873, Pr = 0.118) 6.9658 0.9385 6.8739 0.9261 0.0311 0.159 0.236 0.194

State 2 (Tr = 0.927, Pr = 0.353) 2.1836 0.8311 2.1142 0.8047 0.0664 0.471 0.681 0.527

Z e (R) V Z
r (R) (1)

e H e IG H e H e IG H

Z (0) e H e IG /RTc H
T,P (R) T,P (1) T,P

/RTc /RTc

The change in enthalpy can be calculated from Eq. (3.6-3). From Example 3.13 Z Thus,
343 eP dT = 1612 J/ mol C

323

From Eq. (1), the work done on the system is 495.7 J/ mol.

e = (0.189) (8.314)(369.9) + 1612 (0.552)(8.314)(369.9) = 495.7 J/ mol H

3.7 WHICH EQUATION OF STATE TO USE? In the low density region, i.e., when either pressure is very low or temperature is very high, gas behavior can be described by the ideal gas equation of state. Outside of this region, one might think of how to choose the "best" equation of state among various alternatives. In other words, similar to the queen in Snow White who asked, "Mirror, mirror on the wall, whos the fairest of them all?" (Martin, 1979). The truncated form of the virial equation of state, Eq. (3.1-9), can be used only for the vapor phase for pressures up to approximately 15 bar. For computational purposes, an equation of state representing both vapor and liquid phases would be ideal. In that respect, cubic equations of state have the advantage. However, no cubic equation of state can provide the P V T behavior in all regions of interest. For example, they usually fail near the critical region. Chapter 4 of the book "The Properties of Gases and Liquids " (Poling et al., 2004) provides the guidelines for selecting an equation of state for P V T properties of pure substances.

71

REFERENCES Gupta, D. and P.T. Eubank, 1997, J. Chem. Eng. Data, 42, 961-970. Lee, B.I. and M.G. Kesler, 1975, AIChE Journal, 21, 510-525. Martin, J.J., 1979, Ind. Eng. Chem. Fund., 18, 81-97. Meng, L., Y.Y. Duan and L. Li, 2004, Fluid Phase Equilibria, 226, 109-120. Peng, D.Y. and D.B. Robinson, 1976, Ind. Eng. Chem. Fund., 15, 59-64. Pitzer, K.S., D.Z. Lippmann, R.F. Curl, C.M. Huggins and D.E. Peterson, 1955, J. Am. Chem. Soc., 77, 3433-3440. Pitzer, K.S., 1977, Phase Equilibria and Fluid Properties in the Chemical Industry, ACS Symposium Series, Vol. 60, pp. 1-10. Poling, B.E., J.M. Prausnitz and J.P. OConnell, 2004, The Properties of Gases and Liquids, 5th Ed., McGraw-Hill, New York. Riedlich, O. and J.N.S. Kwong, 1949, Chem. Rev., 44, 233-244. Soave, G., 1972, Chem. Eng. Sci., 4, 1197-1203. Strelzho, S. and L.C. Pan, 1968, Chemical Engineering, 75 (Nov. 4), 191. Tsonopoulos, C., 1979, Adv. Chem. Ser., 143-162. Valderrama, J.O., 2003, Ind. Eng. Chem. Res., 42, 1603-1618. van der Waals, J.D., 1873, Over de Continuiteit van de Gas-en Vloeistoftoestand, Doctoral Dissertation, Leyden. Van Ness H.C. and M.M. Abbott, 1982, Classical Thermodynamics of Nonelectrolyte Solutions, McGraw-Hill, New York.

PROBLEMS Problems related to Section 3.1 3.1 Calculate the second virial coecient for n-butane at 375 K. The experimental value is 426.5 cm3 / mol (Gupta and Eubank, 1997). Also estimate the density of n-butane at 375 K and 5 bar. (Answer: 430.8 cm3 / mol, 0.01 g/ cm3 ) 3.2 Various correlations are available in the literature to calculate the second virial coecient for nonpolar uids besides Eq. (3.1-10). For example, Meng et al. (2004) modied the wellknown Tsonopoulos (1979) correlation as i RTc h (0) B= f + f (1) (1) Pc 72

0.30252 0.15668 0.00724 0.00022 (2) 2 3 8 Tr Tr Tr Tr 0.15581 0.38183 0.44044 0.00541 + (3) f (1) = 0.17404 2 3 8 Tr Tr Tr Tr Calculate the second virial coecients for methane, ethane, and carbon dioxide at 300 K using Eq. (1). f (0) = 0.13356 (Answer: 42.098 cm3 / mol, 181.483 cm3 / mol, 121.869 cm3 / mol) 3.3 Saturated isobutane vapor at 320 K is contained in a piston-cylinder assembly. It is expanded to 3 bar by a reversible isothermal process. At 320 K, the vapor pressure of isobutane is 6.243 bar. Using the virial equation of state, Eq. (3.1-9), a) Estimate the molar volume of isobutane at the initial and nal states, b) Determine the work done during the expansion process. (Answer: a) 3704 cm3 / mol, 8310.7 cm3 / mol b) 1949.7 J/ mol) 3.4 If a gas obeys the virial equation of state, Eq. (3.1-9), use Eq. (1) of Problem 2.1 and show that the Joule-Thomson coecient is given by dB B T dT ! = (1) 2B d e T C P P dT 2 Substitute Eq. (3.1-10) into Eq. (1) to obtain Tc 1.0972 0 . 8944 + 0.139 + 0.083 + 1.6 4.2 Pc Tr Tr = ! e C 1.75552 3.75648 P + Pr + 2.6 5.2 R Tr Tr 3.5 Analytical calculation of the roots of a quadratic equation x3 + p x2 + q x + r = 0 is as follows: Let the terms M and N be dened as M= 3 q p2 9 and N= 9 pq 27 r 2 p3 54 (2) (1)

where

If p, q, and r are real and if = M 3 + N 2 is the discriminant, then > 0; one root is real and two are complex conjugate, = 0; all roots are real and at least two are equal, < 0; all roots are real and unequal.

73

Case (i) Solutions for > 0 In this case the roots are given by x1 = S + T x2 = x3 = where S= 1 p 3 (3) (4) (5)

1 1 1 (S + T ) p + i 3 (S T ) 2 3 2 1 1 1 (S + T ) p i 3 (S T ) 2 3 2 and T = q 3 N

Case (ii) Solutions for < 0 The roots are given by

q 3 N+

(6)

1 o + (i 1)120 p xi = 2 M cos 3 3 where = arccos s N2 ( M )3

i = 1, 2, 3

(7)

( is in degrees)

(8)

In Eq. (7) the upper sign applies if N is positive, while the lower sign applies if N is negative. If methanol obeys the van der Waals equation of state, predict the density of saturated methanol vapor at 11 bar and 413 K analytically. (Answer: 0.01106 g/ cm3 ) 3.6 Estimate the molar volumes of saturated liquid and vapor for n-octane at 293 K using: a) Redlich-Kwong equation of state, b) Soave-Redlich-Kwong equation of state, c) Peng-Robinson equation of state. At 293 K, the vapor pressure of n-octane is 1.387 bar. (Answer: a) 196.9 cm3 / mol, 15, 250 cm3 / mol b) 189.6 cm3 / mol, c) 168.6 cm3 / mol, 14, 540 cm3 / mol) 14, 560 cm3 / mol

3.7 The maximum pressure, P , that a spherical tank can withstand is dependent on the tank radius, R, the wall thickness, tw , and the maximum tensile strength of the material, . The equation proposed by Strelzo and Pan (1968) states that 2t w if P < 0.665 R + 0.2tw 2 P = 2 tw + 1 2 R if P > 0.665 2 tw +1 +2 R where P is the internal gauge pressure. 74

Estimate the maximum amount of ethylene that can be stored in a spherical tank at 300 K. The tank is made of stainless steel 316, has a radius of 1.5 m, and has a wall thickness of 13 mm. Ethylene is represented by the Peng-Robinson equation of state. For stainless steel 316, = 586 MPa. (Answer: ) 3.8 A rigid tank contains propane at 350 K and an unknown pressure. When the tank is cooled to 303 K, the vapor starts condensing. Estimate the initial pressure in the tank using the Peng-Robinson equation of state. At 303 K, the vapor pressure of propane is 10.84 bar. (Answer: 13.234 bar) 3.9 A 0.8 m3 rigid tank contains 2 kg of acetylene at 200 K. Determine the state and pressure of acetylene in the tank using the Peng-Robinson equation of state. The vapor pressure of acetylene at 200 K is 1.905 bar. (Answer: 1.544 bar) 3.10 A 0.05 m3 piston-cylinder device contains 7 moles of isobutane at 350 K. It is compressed isothermally until the volume becomes 0.01 m3 . The vapor pressure of isobutane is given as a function of temperature as 4577.132 + 73.51351 + 1.514279 105 T 2 T where P vap is in kPa and T is in K. Estimate the initial and nal pressures using the PengRobinson equation of state. (Answer: 3.812 bar, 12.469 bar) ln P vap = 9.416723 ln T 3.11 Suppose that a rigid cylinder contains propylene at 380 K and 150 bar. The contents of the cylinder are cooled to 285 K and part of the liquid that condensed at the bottom of the cylinder is removed. If the cylinder temperature is again increased to 380 K, will the pressure be greater than, equal to, or less than 150 bar? Explain clearly. (Answer: Less than 150 bar) 3.12 A piston-cylinder assembly contains 3 kg of acetone with 60% quality. The system is heated at constant pressure until all the acetone vaporizes. Calculate the work done if the temperature at the nal state is 400 K. Assume acetone is represented by the Peng-Robinson equation of state. The vapor pressure of acetone is given as a function of temperature as ln P vap = 10.0311 where P vap is in bar and T is in K. (Answer: 58, 598 J) 2940.46 T 35.93

3.13 From Figure 3.3-a, conclude that the isotherm satises the following equation in the two-phase region: Z V eV vap e V L e e P dV (1) P (V V ) =
eL V

a) If a substance is represented by the Redlich-Kwong equation of state, show that Eq. (1) takes the form ! # " e L + b) eV b e V (V V a V eV V e L ) = RT ln P vap (V ln (2) e V + b) eL b e L (V b T V V 75

b) Express Eq. (2) in terms of dimensionless quantities to obtain V L V Z (Z + B ) A Z B V L + ln =0 Z Z ln B ZL B Z L (Z V + B )

(3)

Note that Eq. (3) can be used to estimate vapor pressures of pure substances at any given temperature. c) Using a trial-and-error procedure, estimate the vapor pressure of propane at 350 K if it obeys the Redlich-Kwong equation of state. (Answer: c) 30.9 bar) Problems related to Section 3.2 3.14 A rigid container is completely lled with 2 kg of mercury at 293 K and 1 bar and sealed. Estimate the amount of heat transferred so as to increase the pressure to 100 bar. The following data are provided for mercury = 13.6 g/ cm3 bP = 0.139 J/ g. K C = 1.82 104 K1 = 3.95 106 bar1

bV 6= C bP . Hint: In this case C (Answer: 507.9 J)

3.15 A piston-cylinder assembly contains 5 moles of carbon monoxide at 300 K. The gas is compressed from 3 L to 1 L by a reversible isothermal process. Calculate the heat removed from the system if carbon monoxide is represented by the van der Waals equation of state. (Answer: 15, 620 J) 3.16 One mole of carbon dioxide undergoes the following changes in a series of nonow processes: (i) From an initial state of 300 K and 4 bar (state 1), it is compressed to 415 K and 15 bar (state 2); (ii) It is then cooled to 325 K at a constant pressure of 15 bar (state 3). For the overall process, the work done on the gas is 320 J. Estimate the heat interaction with the surroundings assuming carbon dioxide obeys the Redlich-Kwong equation of state. (Answer: 184 J) 3.17 A vertical cylinder tted with a frictionless piston contains 1 mole of acetylene at 330 K and 20 bar. The piston-cylinder assembly is well insulated and a mechanical lock prevents the piston from rising. The piston has a mass of 500 kg and a cross-sectional area of 0.02 m2 . The ambient pressure is 1 bar. The mechanical lock is now released. If acetylene obeys the Peng-Robinson equation of state, estimate the gas temperature when the system reaches equilibrium. Take g = 10 m/ s2 . (Answer: 267.7 K) 3.18 Consider a closed system undergoing a reversible adiabatic expansion from state 1 to state 2. a) Starting with T e V e ! e! V S = 1 T e e e S S
T V

(1)

76

show that

b) If an ideal gas with constant heat capacity undergoes an isentropic process, show that Eq. (2) reduces to 1 e1 T2 V = (3) T1 e V 2 e . e /C where = C P V Problems related to Section 3.3

T e V

e S

T e C V

P T

(2)

e V

3.19 A gas at T1 and P1 is throttled to a pressure P2 . It is represented by the virial equation of state, Eq. (3.1-9), with the parameter B dependent on temperature in the form B =+T e is assumed constant, show that the outlet temperwhere and are known constants. If C P ature is given by (P1 P2 ) T2 = T1 + e C
P

3.20 If a gas is represented by the Peng-Robinson equation of state, use Eq. (3.3-10) and show that 1 A ! + e Z B Z (Z + B ) + B (Z B ) V R = T P 1 2 A (Z + B ) P 2 (Z B )2 Z (Z + B ) + B (Z B ) where is dened by Eq. (3.2-20).

3.21 Calculate the change in molar enthalpy when isobutane gas is compressed from 350 K and 10 bar to 450 K and 90 bar in a steady-ow compressor. Use the Peng-Robinson equation of state. (Answer: 2431 J/ mol) 3.22 It is proposed to preheat a gas from 303 K to 398 K in a heat exchanger. The pressure of the gas at the inlet is 35 bar and the pressure drop in the heat exchanger may be considered negligible. Estimate the amount of heat required in J/ mol using the following data aP Z =1+ T with a = 0.02 K1/2 / bar

e is in J/ mol. K, and T is in K. where C P (Answer: 2103 J/ mol)

eP = 11.7 + 0.03 T C

3.23 A vertical cylinder tted with a frictionless piston contains 0.15 m3 of nitrogen at 350 K. The piston has a mass of 250 kg and a cross-sectional area of 0.1 m2 . The piston and cylinder 77

do not conduct heat, but heat can be added to the gas by a heating coil. The ambient pressure is 1 bar and the acceleration of gravity is 10 m/ s2 . Assume that nitrogen is described by the e = 2.5R. If 2 kJ of energy is supplied to nitrogen Redlich-Kwong equation of state with C V through a heating coil, estimate the nal temperature and pressure for the following two cases: a) Stops placed at the initial equilibrium position of the piston prevent it from rising, b) Piston moves freely within the cylinder. (Answer: a) 365 K, 1.32 bar b) 360.6 K, 1.25 bar) Problems related to Section 3.4 3.24 Using the van der Waals equation of state show that P R = T V e b e V

(1)

e R into Eq. (3.4-11) to obtain e = C Substitute Eq. (1) and C V P Z T2 C e e T1 (V2 b) P e dT S = R ln + T T1 e b) T2 (V 1 Show that the substitution of e = ZRT V P and b= BRT P

(2)

(3)

into Eq. (2) leads to Eq. (3.4-13).

3.25 A piston-cylinder assembly initially contains 5 moles of n-pentane at 500 K and 3 bar. The gas is compressed isothermally to 30 bar with a work input of 10 kJ. During this process, heat transfer takes place with the surroundings at a temperature of 298 K. Is this process reversible, irreversible, or impossible? Assume that n-pentane obeys the Peng-Robinson equation of state. (Answer: Impossible) 3.26 Steam enters an adiabatic turbine at 70 bar and 873 K and leaves at a pressure of 4 bar. Estimate the maximum amount of work that can be delivered by the turbine if steam obeys the Peng-Robinson equation of state. (Answer: 15, 190 J/ mol) 3.27 A chemical plant is in need of ethylene at 325 K and 15 bar. Since the available ethylene is at 480 K and 50 bar, two schemes have been suggested to decrease the temperature and pressure of ethylene to the desired values. In Scheme I, ethylene is rst throttled from 50 bar to 15 bar and then sent to the heat exchanger to decrease its temperature to 325 K. In Scheme II, ethylene is rst expanded in a reversible and adiabatic turbine to 15 bar and then sent to the heat exchanger. If ethylene obeys the Peng-Robinson equation of state, determine the heat transfer and work per unit mass of ethylene in each of the suggested schemes. b = 131.4 J/ g) c=0 Q b = 279.6 J/ g; Scheme II: W c = 148.2 J/ g Q (Answer: Scheme I: W 78

Problem related to Section 3.5 3.28 Estimate the volume of a cylinder holding 150 moles of methane at 300 K and 40 bar using the principle of corresponding states. (Answer: 0.0876 m3 ) Problems related to Section 3.6 3.29 If a gas is represented by the virial equation of state, show that the enthalpy and entropy departures are given by " !# e H e IG H 0 . 139 0 . 083 1 . 0972 0 . 8944 T,P = Pr + (1) 2.6 5.2 RT Tr Tr Tr Tr ! eS eIG S 0 . 6752 0 . 7224 T,P = Pr + (2) 2.6 5.2 R Tr Tr Ammonia at 350 K and 15 bar enters a throttling valve and leaves it at 1 bar. Estimate the exit temperature using the virial equation of state. (Answer: 331.13 K) 3.30 Calculate the departure functions for internal energy, enthalpy, and entropy for propane at 400 K and 80 bar using a) van der Waals equation of state, b) Redlich-Kwong equation of state, c) Peng-Robinson equation of state. (Answer: a) 5164 J/ mol, 7035 J/ mol, 12.597 J/ mol. K b) 6956 J/ mol, 8941 J/ mol, 17.245 J/ mol. K c) 7645 J/ mol, 9673 J/ mol, 18.861 J/ mol. K) 3.31 A gas is represented by the following equation of state: P b Z =1+ a T RT where a = 15 106 m3 / mol and b = 0.06 m3 . K/ mol. a) Show that the departure functions for enthalpy and entropy take the form e H e IG eS eIG H S T,P T,P = A 2B and = B RT R where the dimensionless parameters A and B are dened by A= aP RT and B= bP RT 2

b) The gas at 573 K and 10 bar expands reversibly and adiabatically in a steady-ow turbine e = 3.5R. to 1 bar. Calculate the work output of the turbine. Take C P (Answer: b) 7916.7 J/ mol) 79

3.32 A well-insulated cylindrical tank of volume 0.1 m3 initially contains oxygen at 50 bar and 300 K. A relief valve is opened and oxygen is allowed to escape at a constant ow rate of 8 mol/ min. If oxygen is represented by the Peng-Robinson equation of state, estimate the temperature and pressure of oxygen in the tank after 10 minutes. Hint: Assume that the oxygen remaining in the tank undergoes a reversible and adiabatic expansion. (Why?) (Answer: 245.3 K, 25 bar) 3.33 A steady-ow turbine compresses ethane from 300 K and 1 bar to 350 K and 50 bar. Use Eqs. (3.6-3) and (3.6-4) to determine the changes in enthalpy and entropy, respectively, if ethane obeys the Peng-Robinson equation of state. (Answer: 101.7 J/ mol, 29.415 J/ mol. K) 3.34 Use Eq. (3.2-9) and show that the departure function for heat capacity at constant volume is given by Z V e 2 P e e e =T dV (1) CV CV 2 T T,P e V eP eP C C Z
e V

Use Eq. (1) in Eq. (2.2-49) and show that the departure function for heat capacity at constant pressure is given by =T 2P T 2 e T dV (P/T )2 e V R (2)

T,P

3.35 The departure function for molar heat capacity at constant volume is dened by IG e U e eV eV C U = C T T,P T,P V e

e V

e) (P/ V T

(1)

a) If a gas is represented by the Peng-Robinson equation of state, show that the use of Eq. (3.6-20) in Eq. (1) leads to " # e eV C C V Z + 1+ 2 B A (1 + ) T,P ln = (2) R 2 8B Z + 1 2 B where is dened by Eq. (3.2-20). b) Combine Eq. (2) with Eqs. (2.2-51) and (3.2-12) to obtain " # e eP C C P Z+ 1+ 2 B A (1 + ) T,P = ln R 2 8B Z+ 1 2 B 2 1 A + Z B Z (Z + B ) + B (Z B ) + 1 (3) 1 2 A (Z + B ) (Z B )2 Z (Z + B ) + B (Z B )2

c) Calculate the departure functions for molar heat capacities at constant volume and pressure for ethylene gas at 300 K and 150 bar if it obeys the Peng-Robinson equation of state. (Answer: c) 6.470 J/ mol. K, 49.506 J/ mol. K) 80

3.36 In a chemical renery, a certain process requires 12 mol/ s of process steam at 2 bar with not less than 97% quality and not more than 15 K superheat. It is proposed to throttle the available steam at 1173 K and 20 bar through an adiabatic valve and then cool it to the required conditions for the process steam. Estimate the minimum duty of heat exchanger using the principle of corresponding states. The vapor pressure of steam is given as a function of temperature as 3816.44 ln P vap = 11.6834 T 46.13 where P vap is in bar and T is in K. (Answer: 394, 296 W)

81

82