Chapter 3 Solutions Engineering and Chemical Thermodynamics

Wyatt Tenhaeff Milo Koretsky Department of Chemical Engineering Oregon State University koretsm@engr.orst.edu

3.1 Since entropy is a state function

s sys = s sys, step1 + s sys, step 2

Step 1 is a constant volume process. Therefore, no work is done. After neglecting potential and kinetic energy effects, the energy balance for a reversible process becomes

u = q du = q cv dT = q
Using the definition of entropy,
final

s sys ,step1 =

initial

q rev
T

T2

cv dT T T1

Step 2 is an isothermal process. For and ideal gas u is zero and the energy balance is (PE and KE neglected)

q = w dq = w
For an ideal gas, the following can be shown

wrev = Pdv =
Therefore,
final

RT dv v

s sys ,step 2 =

initial

qrev
T

v2

v1

v dv = R ln v

v2 1

Combination of both steps yields

T2

s sys =

T1

v2 cv dT + R ln v T 1

3.2 Equation 3.62 states

T2

s sys =

T1

cP

P2 dT R ln P 1

Substituting the equation for c P yields

T2

s sys =

T1

P2 A + BT + CT 2 dT R ln P T 1

P2 T2 C 2 2 ( ) B T T T T R ln + + s sys = A ln 2 1 2 1 P T 2 1 1

3.3 Equation 3.3 states

S univ = S sys + S surr

where
2 s 1 ) S sys = m( s

S surr =

Qsurr Tsurr

(the temperature of the surroundings is constant)

First, we will calculate S sys . From the steam tables:

kJ 1 = 7.1228 s kg K

(300 C, 10 bar)

Since the container is rigid and mass is conserved in the process,

2 = v 1 v

m3 1 = 0.25794 v kg m3 2 = 0.25794 v kg

(300 C, 10 bar)

To find the number of phases present in state 2, compare the specific volume of state 2 to the specific volume for saturated water and saturated water vapor at 1 bar. From the steam tables,

m3 l , sat 2 v = 0.001043 kg m3 v, sat 2 v = 1.6940 kg

(sat. H2O(l) at 1 bar)

(sat. H2O(v) at 1 bar)

l , sat v, sat 2 2 < v 2 Since v , two phases are present. The quality of the water can be calculated as <v follows

l , sat v, sat 2 = (1 x )v 2 2 + xv v

Therefore,

x = 0.152

From the steam tables:

kJ l , sat 2 s = 1.3025 kg K kJ v, sat 2 s = 7.3593 kg K

(sat. H2O(l) at 1 bar) (sat. H2O(v) at 1 bar)

The entropy of state 2 can be calculated using the following equation:

l , sat v, sat 2 = (1 x )s 2 2 + xs s

kJ 2 = 2.2231 s kg K

Now the entropy change of the system can be calculated.

kJ kJ kJ = 49.0 S sys = (10 [kg ]) 2 . 2231 7 . 1228 K kg K kg K

To find the change in entropy of the surroundings, an energy balance will be useful. Since no work is done, the energy balance is

U = Q
We also know

Qsurr = Q
To following expression is used to solve for the internal energy:
l , sat v, sat 2 1 U = m (1 x )u + xu 2 u

[(

) ]

From the steam tables

kJ 1 = 2793.2 u kg kJ l , sat 2 u = 417.33 kg

(300 C, 10 bar) (sat. H2O(l) at 1 bar)

 kJ v, sat 2 u = 2506.1 kg

(sat. H2O(v) at 1 bar)

The expression for internal energy yields

U = 20583.77 [kJ ]

Therefore,
Q = 20583.77 [kJ ]

and
S surr = Qsurr 20583.77 [kJ ] kJ = = 70.25 Tsurr 293 [K ] K

Now the change in entropy of the universe can be calculated

kJ kJ kJ S univ = S sys + S surr = 49.0 + 70.25 = 21.25 K K K Since Suniv > 0, this process is possible.

3.4 Entropy Balance:

S univ = S sys + S surr

Considering the copper block to be the system, no work is done on the system; thus, the energy balance is

du = q cv dT = q

(neglecting PE and KE)

This can be used in the following expression for entropy

T2

s sys = s sys =

q rev
T cv dT

T1 T2 T1

From Table A.2.3

c P = 2.723R cv = c P = 2.723R

(for liquids and solids)

Therefore,
T2

s sys =

T1

T2 2.723R J 280 [K ] dT = 2.723R ln 8.314 = 2.723 ln T mol K 373.15 [K ] T1

J s sys = 6.50 mol K 10 [kg ] J J 6.50 = 1024 S sys = kg mol K K 0.063465 mol
Since the temperature of the lake remains constant, the change in entropy of the surroundings can be calculated as follows
S surr = Qsurr nCu c P (T2 T1 ) 2.723nCu R(T2 T1 ) Q = = = Tsurr Tsurr Tsurr Tsurr

 J (280 [K ] 373.15 [K ]) 8.314 2.723 10 [kg ] mol K S surr = kg 280 [K ] 0.063546 mol J S surr = 1184 K From the definition of entropy: J J J S univ = S sys + S surr = 1024 + 1184 = 160 K K K

3.5 (a) Since the process is adiabatic and reversible,

S sys = 0

(b) The change in entropy is calculated by

kJ (1 mol) 8.2 mol J = = 73.9 111 K K

liquid

S sys = n

vapor

qrev
T

n h Tb

vap

The sign is negative because there is less randomness in the liquid phase.
(c) For this situation
q = c P dT

Therefore,

S sys = m
Ti

Tf

q rev
T

J 273.15 K cP ( ) dT 18 . 0148 g 4 . 2 = g K ln T 373.15 K 373.15 K

273.15 K

J S sys = 23.6 K The sign is negative because as the water cools, less translational energy states are occupied by the molecules. Therefore, the randomness decreases.
(d) First, calculate the temperature at which the blocks (block A and block B) equilibrate. The energy balance for the process is
n Ac P (T2 373.15 K ) + n B c P (T2 473.15 K ) = 0

Since the heat capacities number of moles of A and B are equal, we find that
T2 = 423.15 K

Now, calculate the change in entropy:

S sys = S sys, A + S sys, B

T T S sys = n Ac P ln 2 + n B c P ln 2 T1, A T1, B Substituting values, we obtain J S sys = 0.337 K The sign is positive because two objects at different temperatures will spontaneously equilibrate to the same temperature when placed together.

10

3.6

The solution below compares problems 2.14 and 2.15, the calculation of 2.13 was erroneously included in the problem statement of the first printing and is shown at the end of this problem.
Problem 2.14 Since the system is well-insulated no heat is transferred with the surroundings. Therefore, the entropy change of the surroundings is zero and
S univ = S sys

The gas in the piston-cylinder system is ideal and c P is constant, so T2 P2 S sys = n c P ln T R ln P 1 1 From the problem statement, we know P 1 = 2 [bar ] P2 = 1 [bar ]

The ideal gas law can be used to solve T1 .

PV (2 [bar ])(10 L ) T1 = 1 1 = = 240.6 [K ] nR L bar 0.08314 mol K (1 [mol]) Solving for T2 is slightly more involved. The energy balance for this system where potential and kinetic energy effects are neglected is
U = W

Conservation of mass requires

n1 = n2 Let n = n1 = n2

The energy balance can be rewritten as

n cv dT = PE dV
T1 V1 T2 V2

11

Since cv and PE are constant ncv (T2 T1 ) = PE (V2 V1 )

V2 and T1 can be rewritten using the ideal gas law

V2 =

nRT2 P2 PV T1 = 1 1 nR

Substituting these expressions into the energy balance, realizing that PE = P2 , and simplifying the equation gives 5 P2 + P 1 V1 2 T2 = 7 nR 2 Using the following values
P 1 = 2 [bar ] V1 = 10 [L] P2 = 1 [bar ]

n = 1.0 [mol] L bar R = 0.08314 mol K

results in
T2 = 206 [K ]

Since both states are constrained, the entropy can be calculated from Equation 3.63:
J 206 [K ] J 1 [bar ] S univ = S sys = (1.0 [mol]) 240.6 [K ] 8.314 mol K ln 3.5 8.314 mol K ln 2 [bar ] J Suniv = S sys = 1.24 K

12

Problem 2.15 Since the initial conditions in the piston-cylinder assembly are equal to the initial conditions of Problem 2.14, T1 and P 1 are known. Moreover, P2 is known, so we only need to find T2 in order to calculate the entropy change. For adiabatic, reversible processes, the following relationship (Equation 2.89) holds:

PV k = const
This can be used to find V2 .
1 P 1 k k V2 = P V1 2

c 7 Noting that k = P = and substituting the proper values results in cv 5

V2 = 16.4 [L]

Th polytropic expression can also be manipulated to yield

TV k 1 = const. Therefore,
T2 = T1V1k 1
k 1 V2

Substitution of the appropriate variables provides

T2 = 197.4 [K ]

Now the entropy can be calculated,

J 1 [bar ] J 197.4 [K ] S univ = S sys = (1.0 [mol]) 8.314 mol K ln 240.6 [K ] ln 3.5 8.314 mol K 2 [bar ]

J S univ = S sys = 0.004 K The value of the entropy shown represents round-off error. Since the process is reversible and adiabatic, we know from Table 3.1 and the related discussion in Section 3.3 that the entropy changes of the system, surroundings, and universe will be zero.
13

Problem 2.13

Equation 3.3 states

2 s 1 ) + S univ = S sys + S surr = m( s
Qsurr Tsurr

where the temperature of the surroundings is constant. First, we will determine s 2 . The first law can be applied to constrain state 2. With potential and kinetic energy effects neglected, the energy balance becomes U = Q + W The value of the work will be used to obtain the final temperature. The definition of work (Equation 2.7) is
W = PE dV
V1 V2

Since the piston expands at constant pressure, the above relationship becomes
W = PE (V2 V1 )

From the steam tables kJ 1 = 6.2119 s (10 MPa, 400 C) kg K m3 1 = 0.02641 v kg (10 MPa, 400 C)

m3 3 1 = (3 kg) 0.02641 V1 = m1v = 0.07923 m kg

[ ]

Now V2 and v2 are found as follows V2 = V1 748740 J W = 0.4536 m3 = 0.07923 m3 6 PE 2.0 10 Pa 3 m3 V2 0.4536 m v2 = = = 0.1512 m2 3 [kg ] kg

[ ]

[ ]

14

2 and P2 are known, state 2 is constrained. From the steam tables: Since v

kJ 2 = 7.1270 s kg K

3 20 bar, 0.1512 m kg

Now U will be evaluated, which is necessary for calculating Qsurr . From the steam tables:
kJ 2 = 2945.2 u kg 3 20 bar, 0.1512 m kg

kJ 1 = 2832.4 u kg

(100 bar, 400 C)

kJ kJ 2 u 1 ) = (3 [kg ]) U = m1 (u 2945.2 kg 2832.4 kg = 338.4 [kJ ]

Substituting the values of U and W into the energy equation allows calculation of Q Q = U W Q = 338400 [J] ( 748740 [J ]) = 1.09 10 6 [J ] = Qsurr

so
2 s 1 ) + S univ = m( s Qsurr Tsurr

kJ 1.09 103 [kJ ] kJ kJ = (3 [kg ]) 6 . 2119 7 .1270 kg K kg K 673.15 [K ] = 1.126 K

Therefore, this process is irreversible.

15

3.7 (a)

From Equation 3.63:

T2 P2 s sys = c P ln T R ln P 1 1 0.5 [bar ] J 7 500 [K ] J s sys = 1 [bar ] = 20.63 mol K 300 [K ] ln 8.314 mol K 2 ln

(b) From Equation 3.65:

T2 v2 s sys = cv ln T + R ln v 1 1 3 0.025 m mol J J 5 500 [K ] = 4.85 8 . 314 ln s sys = + ln m 3 mol K mol K 2 300 [K ] 0 . 05 mol

(c) First, we can find the molar volume of state 1 using the ideal gas law.

v1 =

m3 RT1 = 0.025 P 1 mol

Now, we can use Equation 3.65

T2 v2 s sys = cv ln T + R ln v 1 1 3 0.025 m J 5 500 [K ] mol = 10.62 J + 8 . 314 ln s sys = ln m 3 mol K 2 300 [K ] mol K 0.025 mol

16

3.8 (i). We wish to use the steam tables to calculate the entropy change of liquid water as it goes from its freezing point to its boiling point. The steam tables in Appendices B.1 B.5 do not have data for subcooled water at 1 atm. However, there is data for saturated water at 0.01 C and a pressure of 0.6113 kPa. If we believe that the entropy of water is weakly affected by pressure, then we can say that the entropy of water at 0.01 C and 0.6113 kPa is approximately equal to the entropy at 0 C and 1 atm. The molar volumes of most liquids do not change much with pressure at constant temperature. Thus, the molecular configurations over space available to the water molecules do not change, and the entropy essentially remains constant. We do not need to consider the molecular configurations over energy since the temperature difference is so slight. So, from the steam tables:

kJ (0 C , 1 atm ) s (0.01 C , 0.6113 kPa ) = 0 s kg K kJ (100 C , 1 atm ) = 1.3068 s kg K Therefore, kJ kJ =s (100 C , 1 atm ) s (0 C , 1 atm ) = 1.3068 s 0 kg K kg K kJ = 1.3068 s kg K (ii). From the steam tables: kJ l (100 C , 1 atm ) = 1.3068 s kg K kJ v (100 C , 1 atm ) = 7.3548 s kg K Therefore, kJ kJ =s v (100 C , 1 atm ) s l (100 C , 1 atm ) = 7.3548 s 1.3068 kg K kg K kJ = 6.048 s kg K The change in entropy for process (ii) is 4.63 times the change in entropy for process (i). There are many ways to reconcile this difference, but think about it from a molecular point of view. In process (i), the available molecular configurations over energy are increased as the temperature increases. As the temperature increases, the molar volume also increases slightly, so the 17

available molecular configurations over space also increase. Now consider process (ii), where the molecules are being vaporized and entering the vapor phase. The molecular configuration over space contribution to entropy is drastically increased in this process. In the liquid state, the molecules are linked to each other through intermolecular interactions and their motion is limited. In the vapor state, the molecules can move freely. Refer to Section 3.10 for a discussion of entropy from a molecular view.

18

3.9 Before calculating the change in entropy, we need to determine the final state of the system. Let the mixture of ice and water immediately after the ice has been added represent the system. Since the glass is adiabatic, no work is performed, and the potential and kinetic energies are neglected, the energy balance reduces
H = 0

We can split the system into two subsystems: the ice (subscript i) and the water (subscript w). Therefore, H = mi hi + mw hw = 0 and mi hi = mw hw

We can get the moles of water and ice. mw = Vw 0.0004 m 3 = = 0.399 [kg ] w v m3 0.001003 kg mw (0.399 [kg ]) = 22.15 [mol] = nw = (MW )H 2O 0.0180148 kg mol mi = 5.55 [mol] ni = (MW )H 2O

[ ]

Now, lets assume that all of the ice melts in the process. (If the final answer is greater than 0 C, the assumption is correct.) The following expression mathematically represents the change in internal energies (cP=cv). ni c P ,i (0 ( )10 C ) h fus + c P ,w (T f 0 C ) = nw c P ,w (T f 25 C ) Note: Assumed the heat capacities are independent of temperature to obtain this expression. From Appendix A.2.3 c P ,i = 4.196 R c P ,w = 9.069 R and kJ h fus = 6.0 mol

19

Substitution of values into the above energy balance allows calculation of Tf. T f = 3.12 C (Our assumption that all the ice melts is correct.) Now, we can calculate the change in entropy. From Equation 3.3 suniv = s sys + s surr Since the glass is considered adiabatic, s surr = 0 suniv = s sys We will again break the system into two subsystems: the ice and the water. The change in entropy of the universe can be calculated as follows S univ = ni si + nw s w The definition of change in entropy is
final

s =

initial

qrev T

Assuming the heat capacities of ice and water are independent of temperature, the expressions for the change in entropy of the subsystems are h fus 276.27 K 273.15 K + c P, w ln si = c P, i ln + 273.15 K 263.15 K 273.15 K 276.27 K s w = c P, w ln 298.15 K Therefore h fus 273.15 K 276.27 K 276.27 K S univ = ni c P, i ln + c P, w ln + + n w c P, w ln 263.15 K 273.15 K 273.15 K 298.15 K Substituting the values used before, we obtain

20

 J Suniv = 6.59 mol

21

3.10 (a) The maximum amount of work is obtained in a reversible process. We also know the entropy change for the universe is zero for reversible processes. From the steam tables

kJ 1 = 6.2119 s kg K kJ 2 = 8.5434 s kg K Using the entropy criterion,

(400 C, 100 bar) (400 C, 1 bar)

2 s 1 ) + S surr Suniv = 0 = m(s

kJ kJ 2 s 1 ) = (0.5 [kg ]) S surr = m(s 8.5434 kg K 6.2119 kg K kJ S surr = 1.1658 K

Since the process is isothermal, we know that the temperature of the surroundings is constant at 400 C. Therefore,
Qsurr kJ = S surr = 1.1658 Tsurr K Qsurr = 784.76 [kJ ]

To find the work obtained, perform an energy balance. An energy balance where potential and kinetic energy effects are neglected is

U = Q + W
We can calculate the change in internal energy from the steam tables, and we also know that Q = Qsurr . From the steam tables: kJ 1 = 2832.4 u kg kJ 2 = 2967.8 u kg Therefore, (400 C, 100 bar) (400 C, 1 bar)

22

2 u 1 ) Q W = m(u kJ kJ W = (0 . 5 [kg ]) 2967 . 8 kg 2832 . 4 kg 784 . 76 [kJ ] W = 717.06 [kJ ]

(b) If steam is modeled as an ideal gas, the change in internal energy is zero. Therefore, the energy balance is

Q = W The work can be found using Equation 2.77 which is developed for reversible, isothermal processes.
P2 W = nRT ln P 1 (0.5 [kg ]) 1 bar J (673.15 K )ln 8.3145 W= mol K 100 bar kg 0.0180148 mol W = 715332 [J ] = 715.3 [kJ ]

Therefore,
Q = 715.3 [kJ ]

and

Qsurr = 715.3 [kJ ]

Since the temperature of the surroundings is constant, kJ S surr = 1.06 K

23

3.11 (a) The initial pressure is calculated as follows

P 1 = Psurr +

2(5000 kg ) 9.81 m/s 2 0.05 m

2

) = 24.6 105 Pa
) = 34.4 105 Pa

Similarly, the final pressure is

P2 = Psurr + 3(5000 kg ) 9.81 m/s 2 0.05 m 2

(b) The temperature should rise, which can be understood by considering an energy balance. Because the system is insulated, the work done by the mass being added to the piston is transformed into molecular kinetic energy. (c) The final temperature can be calculated with an energy balance:
U = W ncv (T2 T1 ) = W

Since the pressure of the surroundings is constant after the block is added to the piston, the work is calculated as follows:
W = P2 (V2 V1 )

Assume ideal gas behavior: V2 = nRT2 P2 V1 = nRT1 = 0.00169 m 3 P 1

Now, we can create one equation with one unknown:

nRT2 n(5 / 2 R )(T2 T1 ) = P2 P V1 2

Substitute values and solve for T2:

T2 = 557 K

24

(d) Since the system is well-insulated

s surr = 0 Use Equation 3.65 to calculate the change in entropy:

T2 V2 T2 T2 P 1 suniv = s sys = cv ln T + R ln V = (5 / 2 R )ln T + R ln T P 1 1 1 1 2

Substituting values, we obtain, J s sys = 0.354 mol K

(e) Because the change in entropy of the universe is equal to change in entropy of the system, which is positive in this situation, the second law is not violated.

25

3.12 (a) To calculate ssys, we need to take the gas from state 1 to state 2 using a reversible process. The process in part a can be drawn as follows:
24.6 bar 500 K rev. adiabatic 34.4 bar 557 K

State 1

State 2 rev. isothermal

PI T I = 557 K State I

We need to find the intermediate pressure, PI where we end up at the temperature in state 2, T2. To find it, we can use the results from pages 78-79 of the text:
(1 k ) / k T1P = TI PI(1 k ) / k = T2 PI(1 k ) / k 1

Therefore, T1 (1 k ) P1 = 35.9 [bar] PI = T 2 If we draw the process on a PT diagram, we get:

40 P I 2 Adiabatic compression Isothermal expansion
k

(I)

1 20 490 T 560

26

The change in entropy can be represented as follows:

s sys = s adiabatic + sisothermal

For the reversible adiabatic process, the change in entropy is zero. Therefore,
s sys = sisothermal

For an isothermal process,

q rev = wrev =
Therefore,
final

RT dP P

s sys =

initial

q
T

=
PI

P2

P2 R J = 0.354 dP = R ln P mol K PI

If we substitute relation (I) in the expression above, we get the same expression in the book:
P2 s sys = R ln P 1 T2 T2 P2 k + (1 k ) R ln T = c P ln T R ln P 1 1 1

(b) For this construction, we use the path diagrammed on the following PT diagram:
40 P

2 Isothermal compression

Isobaric heating 1 20 490 T 560

We write

27

s sys = sisobar + sisothermal

First, find an expression for the isobaric heating

q rev = dh = c P dT
Therefore,
T2

sisobar =

T1

2 TP dT = c P ln T 1

Now, we need an expression for the isothermal, reversible expansion

q rev = wrev = Pdv

Therefore,
v 2 = RT2 / P2

sisothermal =

v I = RT2 / P1

P dv = T

v 2 = RT2 / P2 v1 = RT2 / P1

P P2 R 1 dv = R ln = R ln P v P 2 1

Combine the two steps:

T2 P2 J s sys = c P ln T R ln P = 0.354 mol K 1 1

(c) For this construction, we use the path diagrammed on the following PT diagram:

28

40 P

2 Isothermal compression Isochoric heating I

1 20 490 T 560

For isochoric heating followed by an isothermal expansion, the entropy can be expressed as follows:
s sys = sisochoric + sisothermal

For the reversible, isothermal expansion, we obtain (refer to Parts (a) and (b) to see how this is derived)
P2 sisothermal = R ln P I However, we can relate the intermediate pressure to the initial pressure through the ideal gas law:

PI P = 1 T2 T1
or
PI = 27.4 [bar]

P2 T2 P2 P2 sisothermal = R ln = R ln R ln P = R ln T P T1 2 P 1 I 1 T1

For the isochoric process:

q rev = cv dT
Therefore,

29

T2

sisochoric =

T1

2 T dT = cv ln T 1

cv

Combining these results:

T2 s sys = (cv + R ) ln T 1 P2 R ln P 1 T2 P2 J = c P ln T R ln P = 0.354 mol K 1 1

Using any of these three reversible paths, we get the same answer!

30

3.13 (a) Since the process is reversible and adiabatic, the entropy change for the process is zero.

s sys = 0
Furthermore, since the process is adiabatic, the changes in entropy of the surroundings and the universe are also zero.
(b) Since this process is isentropic (s=0), we can apply an expression for the entropy change of an ideal gas.
T2 c P s = 0 = P dT R ln 2 P1 T T
1

Insert the expression for cP from Appendix A

s = 0 = R

T2

P2 3.639 + 0.506 10 3 T 0.227 10 6 T 2 dT R ln P T 1 T1

which upon substituting

T1 = 250 [K ] P1 = 1 [bar ] P2 = 12.06 [bar ]

yields
T2 = 482 [K ]

(c) An energy balance gives

w = u = cv dT =
T1

T2

T2

T1

(c

1)dT

31

 J w = R (2.639 + 0.506 10 3 T 0.227 10 6 T 2 )dT = 5390 mol T1

T2

(d) Reversible processes represent the situation where the minimum amount of energy is required for compression. If the process were irreversible, more work is required, and since the process is adiabatic, the change in internal energy is greater. Since the change in internal energy is greater, so too is the change in temperature. Therefore, the final temperature would be higher than the temperature calculated in Part (b).

32

3.14 The problem statement states that the vessel is insulated, so we can assume that heat transfer to the surroundings is negligible. Therefore, the expression for the entropy change of the universe is
suniv = s sys

An energy balance will help us solve for the entropy change. Neglecting potential and kinetic energy effects, the energy balance is

U = Q + W
Since the vessel is insulated, the heat term is zero. Furthermore, no work is done, so the energy balance is
2 u 1 ) = 0 U = m(u u1 = u 2

The values for the initial pressure and temperature constrain the value of specific energy at state 1. From the steam tables,

kJ 1 = 2619.2 u kg kJ 2 = 2619.2 u kg

(400 C, 200 bar)

The problem statement provides the pressure of state 2 (100 bar). Since we know the pressure and internal energy at state 2, the entropy is constrained. Information given in the problem statement also constrains state 1. From the steam tables,

kJ 1 = 5.5539 s kg K kJ 2 = 5.7754 s kg K
Therefore,

(400 C, 200 bar)

kJ 100 bar, u = 2619 . 2 2 kg

kJ univ = s sys = s 2 s 1 = 0.2215 s kg K kJ S univ = S sys = 0.2215 K

33

3.15 The subscript 2 refers to the final state of the system. 1 refers to the gas initially on one side of the partition. If you take the system to be the entire tank (both sides of the partition), then no net work is performed as the gas leaks through the hole. Furthermore, the tank is well insulated, and kinetic and potential energy effects can be neglected. Thus, the energy balance is
u = 0

and
T2 = T1

(ideal gas)

Initially, the partition is divided into two equal parts. The gas fills the entire volume for the final state ( V2 = 2V1 ). The ideal gas law can be used to calculate the moles of gas present.

n=

P1V1 (10 105 [Pa ])(0.5 m 3 ) = 200.5 mol = RT1 J (300 [K ]) 8.314 mol K

[ ]

Now, the change in entropy can be solved using a slight modification of Equation 3.65:

3 nv 2 T2 v 2 T2 R n R R ln ln ln + = + S sys = n cv ln nv T v T 2 1 1 1 1 J 3 S sys = (200.5 mol) 2 ln(1) + ln(2) 8.314 mol K J S sys = 1155 K

34

3.16 (a) A schematic of the process is shown below:

1 bar, 298 K 1 bar, 298 K P2, T2

N2 N2 N2 N2

N2 N2

O2

Mixing Process

N2

N2 O2

N2

N2 N2 N2 O2 O2

N2 N2 N2

N2

The tank is insulated. The change in entropy of the universe can be rewritten as
S univ = S sys, N 2 + S sys, O2

since the tank is well-insulated. After the partition ruptures, the pressure and temperature will remain constant at 1 bar and 298 K, respectively. This can be shown by employing mass and energy balances. Therefore, the partial pressures in the system are

p2, N 2 = 0.79 bar p2,O2 = 0.21 bar

Use Equation 3.62 to determine the entropies:
298 K

s sys, N 2 =

P2 cP J 0.79 bar ln dT R ln 1 bar 8.314 mol K T P = 1 N 298 K 2

J s sys, N 2 = 1.96 mol K

298 K

s sys, O2 =

P2 cP J 0.21 bar = 8.314 dT R ln ln 1 bar T P mol K 1 O 298 K 2

J s sys ,O2 = 12.98 mol K

Therefore,

J J S univ = (0.79 mol) + (0.21 mol) 1.96 mol K 12.98 mol K

35

J S univ = 4.27 K
(b) A schematic of the process is shown below:
2 bar, 298 K 1 bar, 298 K P2, T 2

N2

N2 N2 N2

N2 N2

N2 N2 N2 O2

Mixing Process

N2

N2 N2

N2 N2

N2 N2

N2 N2 O2 N2

N2 N2

N2 N2 N2

N2 N2

O2

N2

O2 N2

N2 N2 N2

N2

Before calculating the change in entropy, we need to find how the temperature and pressure change during the process. The energy balance simplifies to
U = 0

which can be rewritten as

(nO

+ n N 2 cvT2 n N 2 cv (298 K ) nO2 cv (298 K ) = 0

Assuming the heat capacities are equal, we can show that

T2 = 298 K

We can find the pressure after the rupture by recognizing that the tank is rigid. Therefore,
VO2 + V N 2 = Vtot

By employing the ideal gas law, we get the following equation (it has been simplified):

nN 2 P 1, N 2

nO2 P 1, O2

(nO

+ nN 2 P2

Substitute values and solve to obtain

P2 = 1.65 bar

Now, use Equation 3.62 to calculate the entropies as was done in Part (a):

36

298 K

s sys, N 2 =

P2 cP J 1.30 bar = 8.314 dT R ln ln 2 bar T P mol K 1 N 298 K 2

J s sys, N 2 = 3.58 mol K

298 K

ssys ,O2 =

P2 cP J 0.347 bar dT R ln = 8.314 ln T mol K 1 bar 1 O2 P 298 K

J s sys ,O2 = 8.8 mol K Therefore, J J S univ = (0.79 mol) + (0.21mol) 3.58 mol K 8.8 mol K J Suniv = 4.68 K

37

3.17 First start with the energy balance for the throttle. Potential and kinetic energy effects can be neglected. During the throttling process, no shaft work is performed and the rate of heat transfer is negligible. Therefore,
=m & 2h & 1h m 2 1

A mass balance allows the energy balance to be simplified to =h h 2 1 From the steam tables: = 3398.3 kJ h 1 kg = 3398.3 kJ h 2 kg Now calculate entropy:
univ = s sys + s surr s

(500 C, 8 MPa)

Since the process is adiabatic, kJ surr = 0 s kg K The steam tables can be used to calculate the change in entropy of the system. kJ 2 = 8.7098 s kg K kJ 1 = 6.7239 s kg K Thus, kJ univ = s sys = s 2 s 1 = 1.9859 s kg K
= 3398.3 kJ 100 kPa, h 2 kg

(8 MPa, 500 C)

38

3.18 For this process to work, conservation of mass and the first and second laws of thermodynamics must hold. The subscript 1 refers to the inlet stream, 2 refers to the cold outlet, and 3 refers to the hot outlet. To test the conservation of mass, perform a mass balance &1 = m &2 +m &3 m

kg kg kg 2 = 0.5 + 1.5 s s s Clearly, the conservation of mass holds. Now test the first law of thermodynamics by writing an energy balance. Since there is no heat transfer or work, the energy balance becomes
+m m & 2h & 3h m 2 3 & 1h1 = 0

(PE and KE effects neglected)

Using the conservation of mass we can rewrite the mass flow rate of stream 1 in terms of streams 2 and 3:
h +m h =0 &2 h &3 h m 2 1 3 1

If we assume that the heat capacity of the ideal gas is constant, the equation can be written as follows:
& 2c & 3c P (T2 T1 ) + m P (T3 T1 ) = 0 m

Therefore, kg kg cP (20 K) = 0 0.5 c P ( 60 K) + 1.5 s s This proves that the first law holds for this system. For the second law to be valid, the rate of change in entropy of the universe must greater than or equal to 0, i.e., dS 0 dt univ Assuming the process is adiabatic, we can write the rate of entropy change of the universe for this steady-state process using Equations 3.48-3.50:
dS & 2s 2 + m & 3s 3 m & 1s 1 = m & 2 (s 2 s 1 ) + m & 3 (s 3 s 1 ) =m dt univ

39

where a mass balance was used. For constant heat capacity, we can calculate the entropy differences using Equation 3.63: 5 T2 P2 P2 T2 s2 s1 = cP ln ln P = R 2 ln T R ln P T 1 1 1 1 5 T3 P3 P3 T3 s3 s1 = cP ln ln P = R 2 ln T R ln P T 1 1 1 1 Applying these relations, we get:
1 dS (2.77 R 0.057cP ) = dt univ MW

Therefore, the second law holds if cP 48.6 R ; this value is far in excess of heat capacity for gases, so this process is possible.

40

3.19 (a)
T1 = 640 oC P1 = 4 MPa V1= 20 m/s Nozzle P2 = 100 kPa V2=?

(b) Since the process is reversible and adiabatic,

J S sys = 0 K
(c) The steam tables can be used to determine the final temperature. From the interpolation of steam table data

kJ 2 = s 1 (640 C, 4 MPa ) = 7.4692 s kg K Now two thermodynamic properties are known for state 2. From the steam tables:
T2 = 121.4 C
kJ P2 = 0.1 MPa, s = 7 . 4692 2 kg K

(d) An energy balance is required to calculate the exit velocity. The energy balance for the nozzle is

+e +e &2 h &1 h K 2 m K 1 0=m

&1 = m & 2 allows the energy balance to be written as Realizing that m

+e K ,2 = h K 1 h e 2 which is equivalent to
r r + 0.5V 2 h V2 = 2 h 2 1

[(

Substituting the following values

41

r m V1 = 20 s

= 2719100 J h 2 kg = 3767000 J h 1 kg yields

(0.1 MPa, 121.4 C) (4 MPa, 640 C)

r m V2 = 1448 s
Note: the velocity obtained is supersonic; however, the solution does not account for this type of flow.

42

3.20 A schematic of the process follows:

Propane in v1 = 600 cm3/mol T1= 350 oC

Turbine

ws Propane P = 1 atm 2 out

Since this process is isentropic (s=0), we can apply an expression for the entropy change of an ideal gas. We must be careful, however, to select an expression which does not assume a constant heat capacity.
T2 c P s = 0 = P dT R ln 2 P1 T T
1

Insert the expression for cP from Appendix A

P2 1.213 + 28.785 10 3 T 8.824 10 6 T 2 s = 0 = R dT R ln P T 1 T1

T2

We can also relate P1 to T1 and v1 (which are known) through the ideal gas law: P1 = RT1 v1

This leaves us with 1 equation and 1 unknown (T2). Integrating:

T2 P2 v1 3 6 2 2 s = 0 = 1.213 ln T + 28.785 10 (T2 T1 ) 4.412 10 T2 T1 ln RT 1 1

Using T1 = 623 K, v1 = 600 cm3/mol, P2 = 1 atm

43

R=82.06 cm3 atm/mol K, we get: T2 = 454 K

To solve for

& W S we need a first law balance, with negligible ke and pe, the 1st law for a steady & n

state process becomes:

& +W & & (h1 h2 ) + Q 0=n S

If heat transfer is negligible (isentropic),
T2 T2 & 2 W S = h2 h1 = c p dT = R 1.213 + 28.785 10 3 T 8.824 10 6 T dT & n T1 T1

integrating:

& W S = R 1.213(T T ) + 14.393 10 3 T 2 T 2 2.941 10 6 T 3 T 3 2 1 2 1 2 1 & n

Substituting
J R = 8.314 mol K T2 = 454 K T1 = 623 K

)]

results in
& W S = 19860 J & n mol

44

3.21 A reversible process will require the minimum amount of work. For a reversible process,

suniv = 0 s sys = s surr

For this process, the change in entropy of the system can be calculated as follows
s sys = sO2 + s N 2

where

sO2 =

T2 (c

P )O2

T1

T
P )N 2

P2 dT R ln P 1

O2

s N 2 =

T2 (c

T1

P2 dT R ln P 1

N2

Since the temperature of the streams do not change, the expressions reduce to

P2 sO2 = R ln P 1 O2 P2 s N 2 = R ln P 1 N2
Therefore,
s surr = R ln P2 P1 P2 + ln P O2 1 N2

Since we are assuming the temperature of the surroundings remain constant at 20 C, q s surr = surr Tsurr where

qsurr = q

45

Therefore,

P P2 2 q surr = Tsurr s surr = RTsurr ln + ln P P 1 O2 1 N2 1 bar J 1 bar ( ) + q surr = 8 . 314 293 . 15 K ln ln 0.21 bar O 0.79 bar N mol K 2 2 J q surr = 4378.2 mol
and

J q = 4378.2 mol
Energy Balance:

& n
in

in in

& +W & =0 &out hout + Q h n S

out

Because the temperature of the oxygen and nitrogen doesnt change in the process, the energy balance per mole of feed becomes wS = q

J wS = 4378.2 mol

46

3.22 (a) Take the entire container to be the system and assume no heat or work crosses the system boundary.

Energy Balance:
U = 0

After the oscillation cease, the temperature and pressure on both sides of the piston will be the same assuming the metallic piston is very thin and the thermal conductivity coefficient is large. Now, lets rewrite the energy balance.

U = n1, A ugas A + n1,B ugas B = 0

or n1, A ugas A + ugas B = 0 n1,B n1, A PA,1VA,1TB ,1 P T = = A,1 B ,1 = 2.41 n1,B PB ,1VB ,1TA,1 2 PB ,1TA,1 since 2V A,1 = VB,1 so
2 3 2.41 R(T2 773.15 K ) + R 5/2 + 1.5 10-3 T dT = 0 2 373.15 K

T2 = 585 K

Mass Balance: n A,1 + n B,1 = n A,2 + n B,2 Using the ideal gas law, we get

47

PA,1VA,1 PB ,1VB ,1 PA, 2VA, 2 PB , 2VB , 2 P2Vtot + = + = RTA,1 RTB ,1 RTA, 2 RTB , 2 RT2 since the pressure and temperature of state 2 are equal on both sides. But Vtot = V A,1 + VB,1 = 3V A,1 Using the volume relationships and simplifying, we get P2 = P 2P T2 A,1 + B ,1 = 585 [K ] 10 [bar ] + 2 1 [bar ] 3 TA,1 TB ,1 3 773.15 [K ] 373.15 [K ]

P2 = 3.56 [bar ]

(b) The container is well-insulated, so

suniv = s sys

The entropy change of the system can be split into two subsystems:

ssys =

n1, A n1,B s gas A + s gas B n1, A + n1,B n1, A + n1,B

Using Equation 3.63 and realizing that c P = cv + R ,

sgas A =
sgas B

T2 2.41 R ln P2 = 1.96 J 2.5 R ln P T 3.41 mol K A,1 A,1

T P2 1 2 3.5 + 1.5 10 3 T = 1.51 J R = dT R ln 3.41 TB ,1 T mol K PB ,1

Therefore,

J J J suniv = ssys = 1.96 + 1.51 = 3.47 mol K mol K mol K

The process is possible.

48

3.23

Equation 3.3 can be modified to show

S univ = S sys + S surr

Lets first calculate S sys . Before this problem is solved, a few words must be said about the notation used. The system was initially broken up into two parts: the constant volume container and the constant pressure piston-cylinder assembly. The subscript 1 refers to the constant volume container; 2 refers the piston-cylinder assembly. i" denotes the initial state before the valve is opened, and f denotes the final state. First, the mass of water present in each part of the system will be calculated. The mass will be conserved during the expansion process. Since the water in the rigid tank is saturated and is in equilibrium with the constant temperature surroundings (200 C), the waters entropy is constrained. From the steam tables,

kJ l 1 v , i = 0.001156 kg kJ v 1 v , i = 0.12736 kg kJ l 1 s , i = 2.3308 kg kJ v 1 s , i = 6.4322 kg P sat = 1553.8 [kPa ] Knowledge of the quality of the water and the overall volume of the rigid container can be used to calculate the mass present in the container.
l v 1 1 V1 = 0.05m1 v , i + 0.95m1 v ,i

(Sat. water at 200 C)

( )

( )

Using the values from the steam table and V1 = 0.5 m 3 provides
m1 = 4.13 [kg ]

[ ]

Using the water quality specification,

49

v m1 = 0.95m1 = 3.92 [kg ] l m1 = 0.05m1 = 0.207 [kg ]

For the piston-cylinder assembly, both P and T are known. From the steam tables
m3 2, i = 0.35202 v kg kJ 2, i = 6.9665 s kg K

(600 kPa, 200 C)

Now enough information is available to calculate the mass of water in the piston assembly. V m2 = 2 = 0.284 [kg ] 2 v Now the final state of the system must be determined. It helps to consider what physically happens when the valve is opened. The initial pressure of the rigid tank is 1553.8 kPa. When the valve is opened, the water will rush out of the rigid tank and into the cylinder until equilibrium is reached. Since the pressure of the surroundings is constant at 600 kPa and the surroundings represent a large temperature bath at 200 C, the final temperature and pressure of the entire system will match the surroundings. In other words, kJ f = s 2, i = 6.9665 s kg Thus, the change in entropy is given by
v l v v l l S sys = (m2 + m1 , i + m1, i ) s f m2 s 2, i m1, i s1, i m1, i s1, i

(600 kPa, 200 C)

Substituting the appropriate values reveals kJ S sys = 3.05 K Now we calculate the change in entropy of the surroundings. Since the temperature of the surroundings is constant,
S surr = Qsurr Q = Tsurr Tsurr

After neglecting potential and kinetic energy effects, the energy balance becomes 50

U = Q + W The change in internal energy and work will be calculated in order to solve for Q. The following equation shows how the change in internal energy can be calculated.
v l v v l l U = (m2 + m1 , i + m1, i )u f m2 u 2, i m1, i u1, i m1, i u1, i

From the steam tables

kJ l 1 u , i = 850.64 kg kJ v 1 u , i = 2595.3 kg

(sat. H2O at 200 C)

kJ f =u 2, i = 2638.9 u kg

(600 kPa, 200 C)

Using these values and the values of mass calculated above,

U = 541.0 [kJ ]

Calculating the work is relatively easy since the gas is expanding against a constant pressure of 600 kPa (weight of the piston was assumed negligible). From Equation 2.7, W = PE dV = PE (V f Vi )
Vi Vf

where
PE = 600000 [Pa ] Vi = 0.1 m 3 + 0.5 m 3 = 0.6 m 3

3 v l V f = (m2 + m1 , i + m1, i )v 2, i = 1.55 m

[ ] [ ]

[ ]

[ ]

2, i was used to calculate V f because the temperature and pressure are the same Note: v for the final state of the entire system and the initial state of the piston-cylinder assembly. The value of W can now be evaluated.
W = 570 [kJ ]

51

The energy balance can be used to obtain Q.

Q = U W = 541.0 [kJ ] ( 570 [kJ ]) = 1111 [kJ ]

Therefore, S surr = and kJ kJ kJ Suniv = S sys + S surr = 3.05 2.35 = 0.70 K K K 1111 [kJ ] kJ = 2.35 473.15 [K ] K

52

3.24 Let the subscript 1 represent the state of the system before the partition is removed. It has two components: component a and component b. Subscript 2 represents the system after the partition is removed.

Mass balance: n1, a + n1, b = n2 Energy balance for the adiabatic process:
U sys = W

n1, a cv, a T2 T1, a + n1, b cv, b T2 T1, b = P V2 V1, a + V1, b

)]

The external pressure, P, for the above energy balance is equal to P1,a. To find the final temperature, first find the volumes using the ideal gas law. (2 [mol]) 8.314 J (300 K ) mol K = 0.05 m 3 (1000 [kg ]) 9.8 m s - 2 0.098 m 2

V1, a =

( [ ]) [ ]

[ ]
[ ]

V2 =

(4 [mol]) 8.314

J T2 mol K = 3.3256 10 4 T2 m 3 2 (1000 [kg ]) 9.8 m s 0.098 m 2

( [ ]) [ ]

Substitute the volumes into the energy balance and solve for T2 : 3 3 (2 mol) 1 105 Pa )[3.3256 10 4 T2 0.15 m 3 ] R (T2 300 K ) + (2 mol) R (T2 300 K ) = ( 2

2 T2 = 360.4 K

To calculate the change in entropy, we can use the following relationship

T2 P2 T2 P2 R n c R ln ln ln + S sys = na c P ln b P T P T P 1 1 b 1 1 a

The only unknown in the above equation is P1,b, so we can calculate it with the ideal gas law:

53

P 1, b =

(2 mol) 8.314

J (300 K ) mol K
3

= 0.5 10 5 Pa

0 .1 m

Substitute values into the expression for entropy and solve:

5 360.4 K 5 360.4 K 1 bar 1 bar ln S sys = (2 mol)R ln + (2 mol)R ln ln 0.5 bar b 1 bar a 2 300 K 2 300 K

J S sys = 3.72 K

54

3.25 First perform an energy balance on the process:

U sys = W

The change in internal energy can be written: U = n A, f u A, f + nB , f u B , f n A,i u A mass balance gives: n A,i = n A , f + nB , f These two expressions can be substituted to give: U = n A, f cv (TA, f Ti ) + nB , f cv (TB , f Ti ) = W Using the ideal gas law and cv =

5 R , we obtain 2 5 5 5 PB, f VB, f + PA, f V A, f PA, iV A, i = W 2 2 2

Now, find an expression for the work

W = PE dV
Vi Vf

The pressure is not constant; its value is given by

k (VB VB ,i ) mg kx mg + = Patm + + A2 A A A 5 5 PE = 1.06 10 + 8.284 10 VB [Pa ] PE = Patm +

Integrating
2 W = 1.06 105VB, f 4.142 105VB ,f

Substituting this expression into the energy balance gives: 5 5 5 2 PB, f VB, f + PA, f V A, f PA,iV A, i = 1.06 105VB, f 4.142 105VB ,f 2 2 2

55

This expression can be simplified by recognizing that PB, f = PA, f and V A, f = V A, i : 5 5 2 PB, f VB, f + V A, i PA, iV A, i = 1.06 105VB, f 4.142 105VB ,f 2 2 We still have two unknowns: PB, f and VB, f . We can eliminate PB, f by writing a force balance for the final state:
PB, f = 1.06 105 + 8.284 105VB, f [Pa ]

Substituting this into the energy balance, we obtain 5 5 2 1.06 105 + 8.284 105VB, f VB, f + V A, i PA, iV A, i = 1.06 105VB, f 4.142 105VB ,f 2 2 Solving for the final volume:
VB, f = 0.268 m 3

)(

and for the final pressure.

PB, f = PA, f = Pf = 1.06 105 + 8.284 105 (0.268) = 3.28 105 Pa

Since the gas in A has undergone an adiabatic, reversible expansion

S sys, A = 0

Therefore,
T2 P2 0 = c P ln T R ln P 1 1 3.28 10 5 Pa J 7 T2 0= 8.314 mol K 2 ln 313.15 K ln 5 7.0 10 Pa

Solve for T2:

T2 = 252 K

56

3.26 A schematic of the process is drawn:

Q surr=69.86 kW Steam in P1 = 60 bar T1 = 500 oC

Turbine
Steam out Tsurr=300 K P2 = 10 bar

(a) and (b) The maximum work occurs for a reversible process. Applying the second law, we get:

dS dS dS = + =0 dt univ dt sys dt surr

or 2 s 1 ) + & (s m

& Q surr =0 Tsurr

Calculate the change in entropy of the surroundings:

kJ 1 = 6.8802 We can look up property values of state 1 from the steam tables s and kgK

= 3,422.13 kJ . Converting the units of mass flow rate gives: h 1 kg

kg 1 [hr ] kg & = m 3,600 [s] = 1.25 s 4,500 hr

so 2 = s 1 s

& kJ Q surr = 6.6939 & Tsurr m kgK

2 and P2) From the steam tables: We now know two properties of steam ( s

T2 = 200 oC

Using the steam tables for superheated steam at 1 MPa, we find that when water has this value of entropy

57

 = 2827.9 kJ h 2 kg Energy balance: h =Q & +W & & h m 2 1 s

Calculate Ws:
kJ kJ h Q & = (1.25 kg/s ) & =m 2827.9 3422.1 ( )69.86 [kW ] & h W s 2 1 kg kg & = 673 [kW ] W s

(c) The isentropic efficiency is defined as follows:

= & ) (W S actual & )reversible (W S

For this situation,

& ) (W S actual = 0.665( 673 [kW ]) = 447.5 [kW ]

(d) The real temperature should be higher since not as much energy is converted into work. (e) Use the energy balance:
h =Q & +W & & h m 2 1 s & & = Q + Ws + h = 69.86 kW + -447.5 kW + 3422.1 kJ = 3008.2 kJ h 2 1 kg kg & 1.25 kg/s m

At 1 MPa, water has this value of enthalpy when

(T2 )actual = 280.2 C

58

3.27 Since the compressor is adiabatic, the energy balance after neglecting potential and kinetic energy becomes

& & (h2 h1 ) = W n S

Using the ideal gas law and Appendix A.2, the above equation becomes
& T2 P V 1 1 & WS = A + BT + CT 2 + DT 2 + ET 3 dT T1
T1

Substituting the following values

5 P 1 = 1 [bar ] = 1 10 [Pa ]

3 & = 1m V 1 s T1 = 293.15 [K ] T2 = 473.15 [K ] A = 3.355; B = 0.575 10 3 ; C = 0; D = 0.016 105 ; E = 0 (Table A.2.2)

gives

& = 218.8 [kW ] W S

This is the work of our real turbine (with 80% isentropic efficiency). We can use the isentropic efficiency to calculate the work of an equivalent 100% efficient process.

compressor = & S reversible (WS )

& ) (W

& ) & (W S reversible = (WS )compressor compressor = (0.8)(218.8 [kW ]) & ) (W S reversible = 175.4 [kW ]

compressor

Since the process is adiabatic, we can use the following equation again to calculate what the final temperature would be in a reversible process.
& T2 P V 1 1 & WS = A + BT + CT 2 + DT 2 + ET 3 dT T1
T1

59

& PV 175400 [W ] = 1 1 T1

T2 T1

(A + BT + CT

+ DT 2 + ET 3 dT

Substituting the values from above and solving for T2 , we obtain

T2, rev = 164.8 K

To obtain the pressure the final pressure for the real compressor, we can calculate the final pressure for the reversible process because the final pressure is the same in both cases. For the isentropic expansion
T2

s = 0 =

P2 dT R ln P T 1 T1

cp

A + BT + CT 2 + DT 2 + ET 3 P2 s = 0 = R dT R ln P T 1 T1
T2

T2 = 438 K P2 3.355 + 0.575 10 3 T 1600T 2 dT ln s = 0 = R [1 bar ] T 293 . 15 K T = 1

Solve for P2:

P2 = 4.16 [bar ]

60

3.28 Isentropic efficiency for a turbine is defined as

(ws )actual (ws )rev

If the rate of heat transfer is assumed negligible, the energy balance for this process is
h +W & & h 0=m 1 2 s

For a reversible, adiabatic process,

s sys = 0

2,rev = s 1 (500 C, 10 MPa ) s

From the steam tables

kJ 2,rev = s 1 = 6.5965 s kg K
l , sat v, sat 2 2 s 2 , a mixture of liquid and vapor exists. The quality of the water can be Since s s calculated as follows
l , sat v , sat 2,rev = (1 x )s 2 2 s + xs

kJ kJ kJ + x 7.3593 6.5965 1 .3025 = (1 x ) kg K kg K kg K x = 0.874

Therefore, l ,sat + xh v ,sat 1 x )h h 2 ,rev = ( 2 2

kJ kJ h 1 0.874 ) 2 ,rev = ( 417.44 kg + 0.874 2675.5 kg kJ h 2 ,rev = 2391.0 kg

Also, from the steam tables, = 3373.6 kJ h 1 kg (500 C, 10 MPa)

61

The reversible work is calculated as:

& ) (W S rev =h &1 m

= 2391.0 kJ 3373.6 kJ = 982.6 kJ h 1 kg kg kg

and the actual work as

& ) (W S actual &1 m

& ) (W kJ S rev = 835 &1 m kg

The exit temperature is calculated by determining the enthalpy of the actual exit state: & ) ( W kJ S actual h2, actual = h1 + = 2538.4 &1 m kg This state is still saturated (although the quality is higher), so the temperature is T2 = 99.6 oC

62

3.29 The subscripts 2 and 3 represent the two outline streams, and 1 represents the inlet stream. First, perform a mass balance:

&1 = n &2 + n &3 = n

2 1 &1 + n &1 n 3 3

Now write the energy balance:

& +W & &1h1 (n &2 h2 + n &3 h3 ) + Q 0=n S

Since the system is insulated and there is no shaft work, the energy balance can be rewritten as: 2 1 &1h2 + n &1h3 n &1h1 = 0 n 3 3 2 (h2 h1 ) + 1 (h3 h1 ) = 0 3 3 Substituting expressions for heat capacity A.2.2, we obtain the following expression:
3 4000 1 4000 3 3.280 + 0.593 10 T + dT + R 3.280 + 0.593 10 3 T + dT = 0 2 2 3 T T 300 K 300 K Solving, we find

2 R 3

400 K

T3 = 100.6 K Now set up an entropy balance for the process. The minimum pressure is required for a reversible process.

2 1 &1s2 + n &1s3 n &1s1 = 0 n 3 3 2 (s2 s1 ) + 1 (s3 s1 ) = 0 3 3 Assuming ideal gas behavior, we can express the changes in entropies using Equation 3.62:
400 K 3.280 1bar 4000 ln s 2 s1 = R dT + 0.593 10 3 + P 3 T T 1 300 K 100.6 K 3.280 1bar 4000 ln s3 s1 = R dT + 0.593 10 3 + P 3 T T 1 300 K

63

Substitute these expressions into the entropy balance and solve for P1:
P 1 = 1.85 bar

64

3.30 A schematic of the process is illustrated below:

reversible

Tsurr = 25 oC Psurr = 1 bar Pure H 2O

Pure H2O P1 = 60 bar T1 = 540 oC m = 5 kg

P2 = 20 bar T 2 = ? oC m = 5 kg

well-insulated

(a) Since the process is adiabatic and reversible,

suniv = 0 s sys = 0 s surr = 0

(b) We can obtain the final temperature using the steam tables.

kJ 1 = 6.999 s kg K kJ 2 = 6.999 s kg K

(540 C, 60 bar) (20 bar)

The pressure and entropy of state 2 can be used to back out T2 from the steam tables.
T2 = 362.5 C

(c) To obtain the value of work, perform an energy balance. The process is adiabatic, and potential and kinetic energy effects can be neglected. Therefore, the energy balance is
2 u 1 ) = W U = m(u

From the steam tables,

kJ 2 = 2881.15 u kg

(362.5 C, 20 bar)

65

 kJ 1 = 3156.12 u kg

(540 C, 60 bar)

Hence,
kJ kJ W = (5 [kg ]) 2881 . 15 3156 . 12 kg = 1373 [kJ ] kg

(d) The specific volume can be found in the steam tables

m3 2 = 0.14173 v kg

Therefore,
m3 3 V2 = (5 [kg ]) 0.14173 = 0.709 m kg

[ ]

66

3.31 A schematic of the process is shown below:

very tiny leak hole Tsurr = 25 oC Psurr = 1 bar

Pure H2O P1 = 60 bar T1 = 540 oC m = 5 kg

Pure H2O P2 = 20 bar T ' 2 = ? oC

well-insulated

In order to leave the system, the gas must do flow work on the surroundings. The initial state is the same as for Problem 3.30 and the final pressures are the same. Since the water only expands against 1 bar, the work is lower than that for the differential process described in Problem 3.30. Thus, this adiabatic process looses less energy, leading to a higher final temperature. Another way to view this argument is to look at this process as a closed system. This depiction is the expansion analog of the compression process depicted for Example 2.5 in Figure E2.5B (page 57). We can represent this process in terms of two latches, one that keeps the process in its initial state at 60 bar and one that stops the expansion after the pressure has reduced to 20 bar. The process is initiated by removal of the first latch and ends when the piston comes to rest against the second latch. Such a process is depicted as Problem 3.31 below. The corresponding reversible process of Problem 3.30 is shown next to it for comparison. Clearly the process on the left does less work, resulting in a greater final temperature.

Problem 3.31
T surr = 25 oC Psurr = 1 bar latches Pure H2O P1 = 60 bar T1 = 540 oC m = 5 kg irreversible Pure H2O P2 = 20 bar T ' 2 = ? oC m = 5 kg
Pure H2O P1 = 60 bar T1 = 540 oC m = 5 kg

Problem 3.30
Tsurr = 25 oC Psurr = 1 bar Pure H 2O P2 = 20 bar T 2 = ? oC m = 5 kg

reversible

well-insulated

67

3.32 (a) Consider the tank as the system.

Mass balance
dm & in m & out = m & in =m dt

Separating variables and integrating:

m2

m1

& in dt dm = m
0

or
& in dt m2 m1 = m
0 t

Energy balance Since the potential and kinetic energy effects can be neglected, the open system, unsteady state energy balance is
dU & +W & & out hout m & in hin + Q = m s dt sys out in

The process is adiabatic and no shaft work is done. Furthermore, there is only one inlet stream and not outlet stream. Therefore, the energy balance simplifies to
dU & in hin =m dt sys

The following math is performed

U2

U1 =0

& dU = m
0

in in

& in dt h dt = hin m
0

2 = m2 h U 2 = m2 u in where the results of the mass balance were used. Thus, 2 = h u in

68

From the steam tables, = 3456.5 kJ h in kg (3 MPa, 773 K)

Now the water in the tank is constrained. From the steam tables:
kJ 2 = 7.743 s kg K m 2 = 0.14749 v kg
3

kJ 3 MPa, u 2 = 3456.5 kg

Compute the change in entropy. An entropy balance gives:

dS dS & in sin = m dt univ dt sys

Integrating with sin constant

& in dt = m2 (s 2 s in m 2 s in ) S univ = m2 s
0 t

From the steam tables:

kJ in = 7.2337 s kg K

(3 MPa, 773 K)

Therefore,
0.05 m 3 kJ kJ kJ 7.743 = 0.173 7.2337 S univ = m 3 K kg K kg K 0.14749 kg

(b) If it tank sits in storage for a long time and equilibrates to a final temperature of 20 C, some or all of the vapor will condense and exchange heat with the surroundings. Let the subscript 3 designate the final state of the water when it has reached a temperature of 20 C. The change in entropy between state 2 and state 3 is given by the following equation

69

3 s 2 ) + S univ = m2 (s

Qsurr T

Let the subscript 3 designate the final state of the water when it has reached a temperature of 20 C. First, find quality of the water. From the steam tables:
m3 sat v3, l = 0.001002 kg m3 sat 3 v = 57 . 79 ,v kg

(sat. water at 20 C)

Calculate the quality as follows:

sat 3 = v 2 = (1 x )v 3 sat v , l + xv3, v

m3 m3 m3 + x 0.14749 = (1 x ) 0 . 001002 57 . 79 kg kg kg x = 0.0025

Now calculate the entropy of state 3

sat 3 = (1 x )s 3 sat s , l + xs3, v

Substitute values from the steam tables:

3 = (1 0.0025) s 0.2966 kJ 3 = 0.3175 s kg K kJ kJ 0 . 0025 8 . 6671 + kg K kg K

Now calculate the amount of heat transferred to the surroundings: 3 u 2 ) Q surr = Q = m2 (u Calculate the internal energy of state 3:
sat 3 = (1 x )u 3 sat u ,l + xu 3,v

Substituting values from the steam tables: 70

 kJ 3 = 89.74 u kg

Therefore,
0.05 m 3 kJ kJ 89.74 3456.5 = 1141 [kJ ] Q surr = m 3 kg kg 0 . 14749 kg

Now calculate the change in entropy of the universe

3 kJ kJ 1141 [kJ ] 0.05 m 0 .3175 7 . 743 = kg K kg K 3 + 293 K m 0.14749 kg kJ = 1.38 K

S univ

S univ

The entropy change for both processes can be fount by adding together the entropy change from Part (a) and Part (b): kJ (S univ )(a) and (b) = 1.55
K

71

3.33 A schematic is given below

valve maintains pressure in system constant v T1 = 200 oC x1 = 0.4 V = 0.01 m3 l

Mass balance
dm & in m & out = m & out =m dt

Separating variables and integrating:

m2

m1

& dm = m
0

out

dt

or
& out dt m2 m1 = m
0 t

Entropy Balance: & & dS Q Q dS surr & = & & S + + = + m s m s univ out out out out Tsurr dt sys Tsurr dt sys Integrating with sout constant
Suniv = m2 s2 m1s1 (m2 m1 )sout Q Tsurr

(1)

From steam tables:

72

 kJ s1 = (1 x)u f + xu g = 0.6 2.3309 + 0.4 6.4323 = 3.9715 kg K kJ kJ s 2 = 6.4323 is the same as sout = 6.4323 = s2 kg K kg K

Thus Equation 1 simplifies to

Suniv = m1 ( s 2 s1 ) Q Tsurr

(2)

Energy Balance to find Q :

dU +Q & & out h = m out dt sys

Integrating
2 m2 u

1 m1u

dU = [
t
0

+Q m & dt = h & & out h & m out out out dt + Qdt

0 0

Substituting in the mass balance and solving for Q

2 m 1u 1 (m 2 m 1 )h Q = m 2u out

To find the mass in each state:

m3 v1 = (1 x)v f + xv g = 0.6 .001 + 0.4 0.1274 = 0.051 kg m3 v2 = 0.1274 kg

V 0.01 m 3 = 0.196 [kg ] m1 = 1 = v1 m3 0.051 kg

[ ]

V and m2 = 2 = v2

0.01 m 3 = 0.0785 [kg ] m3 0.1274 kg

[ ]

From the seam tables:

73

 kJ u1 = (1 x)u f + xu g = 0.6 850.64 + 0.4 2597.5 = 1549 kg kJ u 2 = 2595.3 kg

and

kJ hout = 2793.2 kg

Plugging in:
= 228 [kJ ] 2 m1u 1 (m2 m1 )h Q = m2u out

Back into Equation 2

kJ 228 kJ Q kg s =0 (6.4323 3.9715) S univ = m1 ( s 2 s1 ) = 0.196 Tsurr s kg K 473 K s Note: Vaporization is reversible if Tsurr = Tsys.

74

3.34 The process can be represented as:

V1 = 1 m3 P1 = 10 bar T1 = 1000 K

Process Work out Q=0

V2 = 10 m3 P2 = ? T2 = ?

State 1 Solving for the number of moles:

PV n = 1 1 = 120.3 mol RT1

State 2

The maximum work is given by a reversible process. Since it is also adiabatic, the entropy change of the system is zero:
T P s = 0 = cP ln 2 R ln 2 T1 P1 5 Since cP = R 2 T2 T 1
5/ 2

P2 nRT2 = P1 V2 P 1

Solving for T2 gives

nR(T )5 / 2 1 T2 = V P 2 1
2/3

= 215 K

An energy balance on this closed system gives:

U = Q + W = W = n c v dT = n (cP R )dT
T1 T1 T2 T2

Solving for work, we get

3 6 W = n R(T2 T 1 ) = 1.18 10 J 2

75

3.35 The maximum efficiency is obtained from a Carnot cycle. From Equation 3.32
T n = 1 C TH

where temperature is in Kelvin. Hence,

n = 1

298.15 K = 0.614 773.15 K

76

3.36 The labeling described in Figure 3.8 will be used for this solution. First, a summary of known variables is provided.

State 1 2 3 4

P (bar) 30 0.1

T (C) 500

From our knowledge of ideal Rankine cycles, the table can be expanded as follows State 1 2 3 4 Thermodynamic State Superheated Steam Sat. Liq. and Vapor Sat. Liquid Subcooled Liquid P (bar) 30 0.1 0.1 30 T (C) 500

The saturation condition constrains state 3. First, start with the turbine. Since the rate of heat transfer is negligible and the expansion occurs reversibly in an ideal Rankine cycle, the following is known
1 = s 2 s

and

h & =m & h W s 2 1 From the steam tables:

kJ 1 = 7.2337 s kg K kJ l 2 = 0.6492 s kg K
kg K = 3456.5 kJ h 1 kg l = 191.81 kJ h 2 kg v h 2 kJ = 2584.6 kg kJ v 2 s = 8.1501

(500 C, 30 bar)

(sat. H2O at 0.1 bar)

(500 C, 30 bar)

(sat. H2O at 0.1 bar)

77

The quality of the water can be calculated as follows

l v 1 = (1 x) s 2 2 + xs s

By substituting the steam table data, we find

x = 0.878

Now the quality can be used for the following expression

= (1 x)h l + xh v h 2 2 2

Substituting the steam table data and the quality calculated above, we get = 2292.7 kJ h 2 kg Therefore,
kJ kJ kg & = W 2292.7 3456.5 s 100 s = 116.38 [MW ] kg kg

At state 3,
= 191.81 kJ h kg 3 m3 v3 = 0.001010 kg

(sat. H2O(l) at 0.1 bar)

Therefore, h = 210.09 [MW ] & =m & h Q C 3 2 Since the molar volume of water does not change noticeably with pressure and the compressor is adiabatic, the work required for compressing the fluid can be calculated as follows
& =m &v 3 (P4 P3 ) W c

m3 & = 100 kg W 0 . 00101 30 105 0.1 105 [Pa ] = 3.02 10 5 [W ] = 0.302 [MW ] c kg s

78

Now we find the rate of heat transfer for the evaporator. For the entire Rankine cycle, Equation 3.84 gives
& +W & +Q & +W & =Q & +W & =0 Q net net C H s C

We have
& = W & & W & Q Q H s C C

Using the values calculated above:

& = 326.2 [MW ] Q H

Equation 3.84:
& =W & W & W net S C & Wnet = 116.08 [MW ]

The efficiency can be calculated with Equation 3.82

= &net = = 0.356 326.02 [MW ] QH

& W

116.08 [MW ]

79

3.37 To make the Rankine cycle more efficient, we need to increase the area that represents the net work in Figure 3.8. This can be done in a variety of ways:

1. Increase the degree of superheating of steam in the boiler. This process is sketched in the upper left hand Ts diagram below. This change reduces the moisture content of steam leaving the turbine. This effect is desirable since it will prolong the life of the turbine; however, if the steam is heated too high, materials limitations of the turbine may need to be considered. 2. Lower the condenser pressure. Lowering the pressure in the condenser will lower the corresponding saturation temperature. This change will enlarge the area on the Ts diagram, as shown on the upper right below. Thus, we may want to consider lowering the pressure below atmospheric pressure. We can achieve this since the fluid operates in a closed loop. However, we are limited by the low temperature off the heat sink that is available.
increase the superheating of steam in the boiler lower the condenser pressure

1new

T 1

wnet 4 3 2new 3new s 4new

wnet

2new s

increase the boiler pressure

2 stage turbine with reheat Turbine 1 Turbine 2 T 1 6 2 3

wnet 4

wnet 4

80

3. Increase the boiler pressure. This will increase the boiler temperature which will increase the area as shown on the bottom left Ts diagram. 4. We can be more creative about how we use the energy available in the boiler. One way is to divide the turbine into two stages, Turbine 1 and Turbine 2, and reheat the water in the boiler between the two stages. This process is illustrated below.
Rankine cycle with reheat W s turbine 1 2 4 QH Boiler 6 5 Wc compressor condenser 3 QC
cooling water

Ws Turbine 2

1
Fuel Air

The pressure in Turbine 1 will be higher than the pressure in turbine 2. This process is schematically shown on the bottom right Ts diagram. This process leads to less moisture content at the turbine exit (desirable) and limits the temperature of the superheat (desirable).

81

3.38 The labeling described in Figure 3.8 will be used for this solution. First, a summary of known variables is provided.

State 1 2 3 4

P (bar) 100 1

T (C) 500

From our knowledge of ideal Rankine cycles, the table can be expanded as follows

State 1 2 3 4

Thermodynamic State Superheated Steam Sat. Liq. and Vapor Sat. Liquid Subcooled Liquid

P (bar) 100 1 1 100

T (C) 500

The saturation condition constrains state 3. First start with the turbine (state 2). Since the rate of heat transfer is negligible and the expansion occurs reversibly in an ideal Rankine cycle, the following is known
1 = s 2 s

From the steam tables,

kJ 1 = 6.5965 s kg K kJ l 2 = 1.3025 s kg K
v 2 s

(500 C, 100 bar)

kJ = 7.3593 kg K

(sat. H2O at 1 bar)

The quality of the water can be calculated as follows

l v 1 = (1 x) s 2 2 + xs s

By substituting the steam table data, we find

x = 0.874

82

States 1, 2, and 3 are constrained; therefore, the enthalpies can be determined using the steam tables. The enthalpy of state 4 can be calculated from Equation 3.80: =h +v h 4 3 l (P4 P3 )
m3 where vl = v3 = 0.001043 since specific volume of liquids are insensitive to pressure kg changes. From the steam tables:

State

kJ 3240.8 kg = (1 x)h l + xh v Note: h 2 2 2

kJ 2391.0 kg

kJ 417.44 kg

kJ 427.8 kg

Equation 3.84:

& & & W net = Q H QC

Therefore,
h +m h =m h + h h & =m & h & h & h W net 1 4 3 2 1 4 3 2

) (

) [(

) (

)]

and

&= m

[(h1 h4 )+ (h3 h2 )]

& W net

100 103 [kW ]

kJ kJ kJ kJ 3240.8 kg 417.5 kg + 427.8 kg 2391.0 kg

kg & = 116.3 m s
Now consider the non-ideal turbine and compressor. Use the definition of isentropic efficiencies:

& ) ( W s turbine = & actual (Ws )reversible h ) & ) & & )(h (W 2 1 reversible S actual = turbine (WS )reversible = turbine (m

83

compressor =
& ) (W C actual

& ) (W C reversible & ) (W C actual h ) & ) & (h ( W m C reversible 4 3 reversible = =

compressor

compressor

Equation 3.84 is used to find the mass flow rate

& =W & W & W net s C

h h 4 3 reversible h & =m & + W h net turbine 2 1 reversible compressor

Substituting the enthalpy values from the table shown above and the efficiency values gives

kg & = 147 m s
A higher flow rate is needed as compared to the reversible process.

84

3.39 The labeling shown in Figure 3.8 will be used for this solution. First, a summary of known variables is provided.

State 1 2 3 4

Thermodynamic State Sat. Vapor

P (MPa) 1.7 0.7

From our knowledge of ideal Rankine cycles, the table can be expanded as follows State 1 2 3 4 Thermodynamic State Sat. Vapor Sat. Liq. And Vapor Sat. Liquid Subcooled Liquid P (MPa) 1.7 0.7 0.7 1.7

The enthalpy of states 1 and 3 can be found using the NIST website. For states 2 and 4, use the following expressions to find the enthalpies = (1 x)h l + xh v h 2 2 2 =h +v (P P ) h 4 3 l (P4 P3 ) = h3 + v 3 4 3 To find x, use the fact that the turbine is isentropic.
1 = s 2 s
l v 1 = (1 x) s 2 2 + xs s

From the NIST website:

J s1 = 146.38 mol K J l = 90.45 s2 mol K J v = 150.07 s2 mol K

(sat. vapor at 1.7 MPa)

(sat. mixture at 0.7 MPa)

By substituting the above values into the entropy relationship, we find

85

x = 0.938

Also, from the NIST website: J h1 = 36046 mol J l = 18416 h2 mol J v = 35353 h2 mol J h3 = 18416 mol 3 5 m v3 = 6.954 10 mol (sat. vapor at 1.7 MPa)

(sat. mixture at 0.7 MPa)

(sat. liquid at 0.7 MPa)

Substituting these values into the expression for h4 and h2 yields J h2 = 34302.9 mol J h4 = 18485.5 mol Equation 3.82 states

rankine =

h2 h1 (h4 h3 ) h1 h4

J J J J 36046 18416 34302.9 18485.5 mol mol mol mol rankine = J J 18485.5 36046 mol mol rankine = 0.095 This efficiency is significantly lower than a conventional power plant.

86

3.40 (a) Using the information in the problem statement and our knowledge of ideal vapor compression cycles, the following table can be created

Thermodynamic P (MPa) State 1 Sat. Mixture 0.12 2 Sat. Vapor 0.12 3 Superheated Vapor 0.7 4 Sat. Liquid 0.7 Note: Refer to Figure 3.9 to review labeling convention. Equation 3.85 states

State

& =n & (h2 h1 ) Q C

which upon combination with Equation 3.89 gives

& =n & (h2 h4 ) Q C

From the NIST website: kJ h2 = 39.295 mol kJ h4 = 24.181 mol Therefore, mol kJ kJ & = Q C 0.5 s 39.295 mol 24.181 mol = 7.557 [kW ]
(b) The power input to the compressor can be calculated with Equation 3.86:

(sat. vapor at 0.12 MPa) (sat. liquid at 0.7 MPa)

& =n & (h3 h2 ) W C

Equation 3.87 states s 2 = s3

87

From the NIST website: J s3 = s2 (sat. vapor at 0.12 MPa ) = 177.89 mol K Now, state 3 is constrained. kJ h3 = 43.031 mol Therefore, mol kJ kJ & = W C 0.5 s 43.031 mol 39.295 mol = 1.87 [kW ]
(c) Equation 3.90 states:

J 0.7 MPa, s3 = 177.89 mol K

kJ kJ 24 . 181 39.295 h h h h mol mol = 4.05 COP = 2 1 = 2 4 = h3 h2 h3 h2 kJ kJ 39.295 43.031 mol mol

88

3.41 Using the information in the problem statement and our knowledge of ideal vapor compression cycles, the following table can be created

Thermodynamic P (MPa) State 1 Sat. Mixture 0.12 2 Sat. Vapor 0.12 3 Superheated Vapor 0.7 4 Sat. Liquid 0.7 Note: Refer to Figure 3.9 to review labeling convention. From Equation 3.90 COP =

State

& Q h h C = 2 1 & WC h3 h2

The enthalpy of state 2 can be found directly from the NIST website, but the enthalpies of states 1 and 3 require the use of additional information. kJ h2 = 39.295 mol (sat. vapor at 0.12 MPa)

For the process between state 2 and state 3, s 2 = s3 From the NIST website: J s3 = s 2 = 177.89 mol K Now, state 3 is constrained. kJ h3 = 43.031 mol J 0.7 MPa, s3 = 177.89 mol K (sat. vapor at 0.12 MPa)

The process between state 4 and state 1 is also isentropic. J s1 = s 4 = 115.09 mol K (sat. liquid at 0.7 MPa)

The quality of the R134a can be calculated as follows

89

l v s1 = (1 x )s1 + xs1

where J l = 90.649 s1 mol K J v s1 = 177.89 mol K Therefore, J J J = (1 x ) 177.89 90.649 + x 115.09 mol K mol K mol K x = 0.280 Using the quality of R134a, the enthalpy of state 1 can be calculated as follows
l v h1 = (1 x )h1 + xh1

(sat. R134a(l) at 0.12 MPa) (sat. R134a(v) at 0.12 MPa)

From the NIST website: kJ l = 17.412 h1 mol kJ v h1 = 39.295 mol Therefore, kJ kJ h1 = (1 0.28) 17.412 mol + 0.28 39.295 mol kJ h1 = 20.74 mol Now, everything needed to calculate COP is available. Using Equation 3.90,
kJ kJ 39.295 20.74 h h mol mol = 4.97 COP = 2 1 = h3 h2 kJ kJ 43.031 39.295 mol mol

(sat. R134a(l) at 0.12 MPa) (sat. R134a(v) at 0.12 MPa)

90

Is this modification practical? No. An isentropic turbine adds significant level of complexity to the cycle. Turbines are expensive and wear over time. Furthermore, the real turbine added to the cycle will not be 100% efficient, so the COP will not increase as much. The cost of the turbine is not justified by the increase in COP.

91

3.42 The subscript h refers to the hotter cycle, while c refers to the cooler cycle. The (a) The flow rate of the cooler cycle can be found by performing an energy balance on the condenser/evaporator shared between the two cycles. An energy balance shows:
& & & Q H , c = QC , h = Q

Written in terms of enthalpy, the equation is

& c (h8 h7 ) = n & h (h2 h1 ) n

We can find the enthalpies for positions 2 and 8 directly from the thermodynamic tables because the fluid is saturated in at these positions. To find the other enthalpies we must use the following relationships: s 6 = s7 h1 = h4 Using the NIST website: J h1 = 24181 mol J h2 = 40967 mol J h7 = 41510 mol J h8 = 21099 mol Now the flow rate can be calculated: J J (0.5 [mol/s]) 40967 mol 24181 mol = J J 21099 mol 41510 mol mol = 0.411 s (sat. R134 liquid at 0.7 MPa) (sat. R134 vapor at 0.35 MPa) J ) (R134 vapor at 0.35 MPa with s = 177.89 mol K (sat. R134 liquid at 0.35 MPa)

&c n

&c n

92

(b) Performing an energy balance we find

& =n & c (h6 h5 ) Q C

We can also use the following relationship J h5 = h8 = 21099 mol From the NIST website: J h6 = 39295 mol Therefore, mol J J & = Q C 0.411 s 39295 mol 21099 mol = 7.48 [kW ]
(c) The power input is calculated as follows:
& & & W C , total = WC , c + WC , h

(sat. R134 vapor at 0.12 MPa)

where
& &c (h7 h6 ) W C,c = n & & h (h3 h2 ) W C,h = n

We have all of the required enthalpies except h3. State 3 is constrained because J s3 = s 2 = 175.95 mol K P3 = 0.7 MPa From the NIST website: J h3 = 42428 mol J ) (R134a vapor at 0.7 MPa with s = 175.95 mol K (sat. R134a vapor at 0.35 MPa)

Now compute the power for each unit:

93

 J J J J & W C , total = 0.411 [mol/s] 41510 mol 39295 mol + 0.5 [mol/s] 42428 mol 40967 mol
& W C , total = 1.64 [kW ]

(d) The coefficient of performance is calculated using the following equation:

COP =

& W C , total

& Q C

7.48 kW = 4.56 1.64 kW

(e) The COP for the cascade is 4.56, while the COP is 4.05 in Problem 3.40. The cascade systems COP is 12.6% greater.

94

3.43 One design follows; your design may differ:

In order to cool a system to -5 C, the temperature of the fluid must be colder than -5 C so that heat transfer will occur. We arbitrarily specify that the working fluid evaporates at -10 C. Similarly, in order to eject heat to the 20 C reservoir, the fluid must condense at a temperature greater than 20 C. Arbitrarily, we choose 25 C. One possible refrigeration cycle is presented below.
valve T 1 evaporator refrigerated unit at -5 C 4 QC QH 2 3 W c compressor condenser 20 C reservoir 1 QC 2 4 QH 3

A number of fluids will work sufficiently for this system, but the design process will be illustrated using R134a. For states 3 and 4, the pressure is constant, and for states 1 and 2, the pressure is constant at a different value. From the NIST website, we find
P (Tsat = -10 C) 1 = P2 = 0.201 MPa P3 = P4 = 0.665 MPa (Tsat = 25 C) (Note: The temperatures of each state are not constant. The listed saturation temperatures are the temperatures at which the fluid evaporates and condenses.)

Now that the pressures are known, we can compute the required flow rate required in order to provide 20 kW of cooling.

& =n & (h2 h1 ) Q C

We can get h2 from the thermodynamic tables for saturated R134a. In order to find h1, we can use the following relationship:
h1 = h4

From the NIST website: J h2 = 40064 mol (sat. R134 vapor at 0.201 MPa)

95

 J h4 = 23931 mol

(sat. R134 liquid at 0.665 MPa)

Now, calculate the required flow rate of R134a.

&= n

& Q 20,000 [J/s] C = (h2 h1 ) J J 40064 mol 23931 mol mol & = 1.24 n s

96

3.44 The schematic of the process and the corresponding Ts is presented below
T = 5 oC Fridge 2 valve 3 T = -15 oC Freezer evaporator QC,F 4 5 Wc compressor QC,R evaporator 6 5 oC QH condenser s high T reservoir -15 oC 2 1 1 QH Wc QC,R 3 QC,F 4 5 valve T 6

A number of refrigerants will work for this system, but the design process will be illustrated for R134a only. To define each state, we need to thermodynamically constrain each state. You should note that the problem doesnt state what temperature the fluid condenses at. Therefore, we can assume the temperature is 25 C. By using information in the Ts diagram and from the NIST website, we find
P 1 = P2 = 0.34966 MPa P3 = P4 = 0.16394 MPa

P5 = P6 = 0.66538 MPa

(T1=T2=Tsat = 5 C) (T3=T4=Tsat = -15 C) (T6 = 25 C)

Before solving for additional pressures and temperatures, we will list the known temperatures and pressures.
State 1 2 3 4 5 6 Temperature (C) 5 5 -15 -15 25 25 Pressure (MPa) 0.24334 0.24334 0.16394 0.16394 0.66538 0.66538

States 4, 5, and 6 are completely constrained as confirmed by Gibbs phase rule. Now, we need to find the liquid and vapor compositions of states 1, 2, and 3 to completely constrain the states. Since the heat duties are equal for the refrigerator and the freezer, we have the following relationship:
& & Q C , F = QC , R

97

which upon performing an energy balance becomes h4 h3 = h2 h1 Energy balances around the valves provide: h1 = h6 h2 = h3 Substituting these relationships into the expression that equates the heat loads results in
h + h6 h2 = h3 = 4 2

From the NIST website: J h4 = 39755 mol J h6 = 23931 mol Now constrain states 1, 2, and 3 by determining the enthalpies: J h1 = h6 = 23931 mol J J + 23931 39755 mol mol = 31843 J h2 = h3 = 2 mol Technically, the states are now all constrained, but we would like also like to know the vapor and liquid compositions of each state. The compositions of states 4, 5, and 6 are already known; we can calculate the compositions of states 1, 2, and 3 as follows:
sat sat h1 = (1 x1 )h1 , l + x1h1, v sat sat h2 = (1 x2 )h2 , l + x2 h2, v sat sat h3 = (1 x3 )h3 , l + x3 h3, v

From the NIST website,

98

 J sat h1 , l = 21095 mol J sat h2 , l = 21095 mol J sat h3 , l = 18380 mol

J sat h1 , v = 40965 mol J sat h2 , v = 40965 mol J sat h3 , v = 39755 mol

Now, we can solve the composition of vapor for each state:

x1 = 0.143 x2 = 0.541

x3 = 0.630

The following table presents a summary of our results:

State Temperature (C) Pressure (MPa) Phases Liquid Vapor Composition Composition

1 2 3 4 5 6

5 5 -15 -15 25 25

0.24334 0.24334 0.16394 0.16394 0.66538 0.66538

Saturated Liquid and Vapor Saturated Liquid and Vapor Saturated Liquid and Vapor Saturated Vapor Superheated Vapor Saturated Liquid

0.857 0.459 0.37 0 0 1

0.143 0.541 0.630 1 1 0

99

3.45 In this case, the working material is a solid. The four states of the magnetic material are shown of the sT diagram below. Note the axis are shifted from the usual manner.

3 2 QC 1 4 QH

(a) The heat expelled by the cold reservoir can be approximated by:

qC TC (s 2 s1 ) where T is the average temperature between states 1 and 2, which is approximately 1 K. Taking values of S/R from the sT diagram, we get: J qC R(1.9 1.3) = 5.0 mol K
(b) Similarly, the heat absorbed by the hot reservoir can be approximated by:

J q H TH (s 4 s 4 ) = 8.8R(1.2 1.9) = 51 mol K

(b) The coefficient of performance is given by:

COP =

qC wC ,total

qC = 0.11 q H qC

(d) The value of COP is much lower than a typical refrigeration process (COP= 4-6); in general, refrigeration processes at these low temperatures are much less efficient.

F. Work is supplied to magnetize the material and to spin the wheel. 100

3.46 When the polymer is unstretched it is in a more entangled state. When stretched the polymer chains tend to align. The alignment decreases the spatial configurations the polymer can have, and therefore, reduces that component of entropy. If the process is adiabatic, the entropy of the system cannot decrease. Consequently, its thermal entropy must increase. The only way this can be accomplished is by increased temperature.

101

3.47 Assume the temperature is 298 K. The following data was taken from Table A.3.2:

Species Cu2O (s) O2 (g) CuO (s)

h f (kJ/mol) -170.71 0 -156.06

g f (kJ/mol) -147.88 0 -128.29

The data listed above were used to create the next table using s f = h f g f T Species Cu2O (s) O2 (g) CuO (s) s f (kJ/mol K) -0.0766 0 -0.0932

Now the change in entropy of the reaction can be calculated in a method analogous to Equation 2.72 kJ kJ s rxn = vi s f = 2 + 4 - 0.0766 - 0.0932 i mol K mol K kJ s rxn = 0.22 mol Does this violate the second law of thermodynamics? This problem shows that the entropy change of the system is negative, but nothing has been said about the entropy change of the universe. We must look at the change in entropy of the surroundings to determine if the second law is violated. By looking at the enthalpies, we see that the reaction is exothermic, which means that heat is transferred from the system to the surroundings. Therefore, the entropy of the surroundings will increase during this reaction.

( )

102

3.48 The temperature and pressure terms in the equation for entropy do not contribute anything to the entropy change because they are constant. Therefore, the only remaining entropy contribution, the randomness of the atomic arrangements, must be considered. The randomness does not increase when CdTe forms. In pure crystals of Cd and Te, the location of each atom is known because the crystal lattice constrains the atomic locations. In CdTe, the crystal lattice still defines the location of each atom, so the randomness has not increased. Therefore, the change in entropy is zero. 3.49 This argument is not scientifically sound. Morris is arguing that since evolution results in more order, the second law of thermodynamics is violated, so evolution must be impossible. However, the flaw in this argument is caused by ignoring the entropy change of the entire universe. The second law states that the entropy of the universe will remain constant or increase for any process. Morris argument was based on the entropy of the system undergoing evolution not the entropy of the entire universe. A system can decrease in entropy if the entropy of the surroundings increases by at least that much.

103

3.50 Entropy is related to the number of configurations that a state can have. The greater the number of configurations, the more probable the state is and the greater the entropy. We can qualitatively relate this concept to the possible hands in a game of poker, but it is more interesting to quantify the results using some basic concepts of probability.

We consider a hand of poker containing 5 cards randomly draw from a deck of 52 cards.. There are a finite number of permutations in which we can arrange a 52 card deck in 5 cards. For the first card in the hand, we select from 52 cards, the second card can be any other card so we select from 51 cards, the third card has 50 cards, and so on. Thus the number of permutations of 5 cards is:

P = 52 51 50 49 48 = 311,875,200
However, we do not care the order in which the cards are dealt, so we must divide this number by the number of ways we can come up with the same hand. We do this math in a similar way. For a given hand there are five cards we can pick first, four we can pick second, . So the number of ways we can make the same hand is:
N = 5 4 3 2 1 = 120

The number of unique configurations can be found by dividing P by N . Thus, the cards can display
C= P = 2,598,960 N

or 2,598,960 unique configurations. To find the entropy of a given hand, we need to find out how many of these unique configurations belong to the hand Consider a four of a kind. There are 13 different possible ranks of four of a kind, one for each number A, 2, 3, 4, 5, 6, 7,8, 9, 10, J, Q, K. The fifth card in the hand could be any of the other 48 cards. Therefore, the number of combinations of four of a kind is: 13 x 48 = 624 The probability of a four of a kind is: 624 / 2598960 = 1 / 4165 which is very unlikely. Thus the entropy of this hand is low. In contrast, there are 1,098,240 to have a hand that has one pair; therefore the probability of getting this hand is much greater, 1/2.4, and its entropy is high. The probability of having nothing is 1/2 which represents the most likely hand in poker, or the hand with the highest entropy. In fact, the rules of poker are defined so the hand of lower entropy always beats the hand of higher entropy.

104