Chapter 5 Solutions Engineering and Chemical Thermodynamics

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

5.1 (a) Following the example given by Equation 5.5a in the text
u u du = dT + dP P T T P

(b) u u du = dT + ds T s s T (c) u u du = dh + ds s h h s

5.2. The internal energy can be written as follows u u du = dT + dv T v v T Substituting Equations 5.38 and 5.40

P u u P = cv and = T v T T v T v
into the above expression yields

P du = cv dT + T P dv T v
From the ideal gas law, we have

R P = T v v
Therefore,

RT du = cv dT + P dv v
which upon noting that P =

RT for an ideal gas, becomes v

du = cv dT

5.3 The heat capacity at constant pressure can be defined mathematically as follows

h u + (Pv ) u v cP = = = + P T T P P T v T P
For an ideal gas:

R v = T P P
Therefore,

u cP = +R T v
One mathematical definition of du is

u u du = dT + dP T P P T u We can now rewrite : T v u u T u P = + = cv T v T P T v P T T v

For an ideal gas:

u =0 P T
so

u cv = T P
Substituting this result into our expression for c P gives

c P = cv + R

5.4 In terms of P, v, and T, the cyclic equation is

P T v 1 = T v v P P T
For the ideal gas law:
Pv = RT

so the derivatives become:

R P = T v v P T = v P R RT v v = 2 = P P T P
Therefore,

P T v R P v = = 1 T v v P P T v R P
The ideal gas law follows the cyclic rule.

5.5 For a pure species two independent, intensive properties constrains the state of the system. If we specify these variables, all other properties are fixed. Thus, if we hold T and P constant h cannot change, i.e.,

h =0 v T , P

5.6 Expansion of the enthalpy term in the numerator results in

Ts + vP h = T s T s P h = v T s T s Using a Maxwell relation s h = v v P T s s T h = v T P v P T s We can show that c s = P T P T

1 RT 2a 2ab T + = v P R v b v 2 v 3

(use thermodynamic web) (differentiate van der Waals EOS)

Therefore, v vc RT 2a 2ab 2a b h = cP + 1 = P 2 3 T s RT v b v v v b vRT v

5.7
h : P T

s Ts + vP h = T + v = P P T T P T
R v s 2 = 1 + B' P + C ' P = P T P P T RT h 1 + B ' P + C ' P 2 + v = v + v = P P T h =0 P T

h : P s h Ts + vP =v = P s P s RT h 1 + B' P + C ' P 2 = P P s

h : T P h = cP T P

(Definition of cP)

h : T s P Ts + vP h = v = T T s s T s c T c P s P P = P = P = T v P T R 1 + B' P + C ' P 2 T P s T T s

Pv 1 1 + B' P + C ' P 2 h = c = c P P RT 1 + B' P + C ' P 2 T s 1 + B' P + C ' P 2 h = cP T s

( (

) )

5.8 (a) A sketch of the process is provided below

well insulated

T1 P1

s = 0 T2 P2

The diagram shows an infinitesimal amount of mass being placed on top of the piston of a piston-cylinder assembly. The increase in mass causes the gas in the piston to be compressed. Because the mass increases infinitesimally and the piston is well insulated, the compression is reversible and adiabatic. For a reversible, adiabatic process the change in entropy is zero. Therefore, the compression changes the internal energy of the gas at constant entropy as the pressure increases.
(b) To determine the sign of the relation, consider an energy balance on the piston. Neglecting potential and kinetic energy changes, we obtain

U = Q + W
Since the process is adiabatic, the energy balance reduces to
U = W

As the pressure increases on the piston, the piston compresses. Positive work is done on the system; hence, the change in internal energy is positive. We have justified the statement

u >0 P s

10

5.9 (a) By definition:

=
and

1 v v T P 1 v v P T

Dividing, we get:
v v P T P = = v T P v T P T

where derivative inversion was used. Applying the cyclic rule:

v P T 1 = T P v T P v

Hence,

P = T v
(b) If we write T = T(v,P), we get:

T T dT = dv + dP P v v P
From Equations 5.33 and 5.36
ds = cv c P v dT + dv = P dT dP T T T v T P

(1)

We can solve for dT to get:

11

dT =

T P T v dP dv + c P cv T v c P cv T P

(2)

For Equations 1 and 2 to be equal, each term on the left hand side must be equal. Hence,

T T = v P c P cv
or

P T v

v P v c P cv = T = T T P T v T P
where the result from part a was used. Applying the definition of the thermal expansion coefficient:

Tv P v c P cv = T = T v T P

12

5.10 We need data for acetone, benzene, and copper. A table of values for the molar volume, thermal expansion coefficient and isothermal compressibility are taken from Table 4.4:

Species Acetone Benzene Copper

m3 v 10 6 mol 73.33 86.89 7.11

103 K -1
1.49 1.24 0.0486

[ ]

1010 Pa -1
12.7 9.4 0.091

[ ]

We can calculate the difference in heat capacity use the result from Problem 5.9b:
c P cv = vT 2

or

73.33 10 6 c p cv =

m3 3 -1 2 (293 K ) 1.49 10 K mol

12.7 10
10

[ ])

[Pa ]
-1

J = 37.6 mol K

Species

Acetone Benzene Copper

J c p cv mol K 37.6 41.6 0.5

J cp mol K 125.6 135.6 22.6

% difference 30% 31% 2%

We can compare values to that of the heat capacity given in Appendix A2.2. While we often assume that cP and cv are equal for condensed phases, this may not be the case.

13

5.11 We know from Equations 4.71 and 4.72

1 v v T P

and

1 v v P T

Maxwell relation: s P = v T T v Employing the cyclic rule gives P P v = T v v T T P which can be rewritten as
1 v v T P P s = = v T T v 1 P v v T Therefore,

s = v T
Maxwell Relation: s v = P T T P From Equation 4.71: v = v T P Therefore, s = v P T

14

5.12 (a) An isochor on a Mollier diagram can be represented mathematically as

h s v This can be rewritten: h Ts + vP P = =T + s s v v s v Employing the appropriate Maxwell relation and cyclic rule results in h T s = T + v s v v T s v We know T T s P and = = s v c v v T T v For an ideal gas: R s P = = v T T v v Therefore,
T R R h 1+ = T =T + v cv v cv s v

(b) In Part (a), we found

T h =T + v cv s v For a van der Waals gas:

P T v

15

R P = T v v b Therefore, RT h =T + cv s v v v b

16

5.13 (a) The cyclic rule can be employed to give

T T s = s P P T P s Substitution of Equations 5.19 and 5.31 yields T T = P s c P For an ideal gas: R v = T P P Therefore, RT 1 v T = = P cP cP P s
(b) Separation of variables provides

v T P

T R P = T cP P Integration provides T2 ln T 1 P2 = ln P 1 cP
R

which can be rewritten as T2 = T1 P1

R P2 cP

The ideal gas law is now employed

17

P2 v 2 P2 cP = P1v1 P1
R 1 c P P2 v

R 1 c P1 P

v 1

where
1

R c P R cv 1 = = = cP cP cP k

If we raise both sides of the equation by a power of k, we find

k k P2 v 2 = P1v1

Pv k = const.
(c) In Part (a), we found

T v T = P s c P T P Using the derivative inversion rule, we find for the van der Waals equation Rv 3 (v b ) v = T P RTv 3 2a(v b )2

Therefore, 1 RTv 3 (v b ) T = P s c P RTv 3 2a(v b )2

18

5.14 The development of Equation 5.48 is analogous to the development of Equation E5.3D. We want to know how the heat capacity changes with pressure, so consider

c P P

which can be rewritten as

c P P h h = = T P T P T T P T P

h Consider the term: P T h Ts + vP s v = T + v = T +v = P P T T P P T T c Substitution of this expression back into the equation for P results in P T
v c P T v + = P T T T P P 2v T v v c P + = T 2 T T P P T T P T P 2v c P = T 2 T P T P

Therefore,
real cP

ideal cP

dc P =

Preal

Pideal

2v dP T 2 T P

and
real ideal = cP cP Preal 2v T 2 Pideal T

dP P

19

5.15 In order to solve this problem we need to relate the change in entropy from 10 to 12 bar to the change in molar volume (for which we have complete data). First, we can rewrite the change in entropy as
12 bar

s = s 2 s1 =

s dP P T 10 bar

Applying a Maxwell relation, we can relate the above equation to the change in molar volume:
12 bar

s 2 = s1 +

s v dP = s1 + dP P T T P 10 bar 10 bar

12 bar

As 10 bar:
v v 4 = 5.60 10 T P T P m3 kg K

At 12 bar:
v v 4 = 4.80 10 T P T P m3 kg K

v To integrate the above entropy equation, we need an expression that relates to pressure. T P Thus, we will fit a line to the data. We obtain
v 10 = 4.0 10 T P m3 3 4 m P + 9.6 10 kg K kg K Pa

Now integrate the equation to find the entropy:

1.210 6 Pa

s 2 = s1 +

1.010 6 Pa

[(4.0 10

10

kJ )P 9.6 10 4 ]dP =5.4960 0.104 kgkJ = 5.392 K kg K

20

5.16 A schematic of the process follows:

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

Turbine

ws Propane P = 1 atm 2 out

We also know the ideal gas heat capacity from Table A.2.1:

cP = 1.213 + 28.785 10 3 T 8.824 10 6 T 2 R Since this process is isentropic (s=0), we can construct a path such that the sum of s is zero.
(a) T, v as independent variables Choosing T and v as the independent variables, (and changing T under ideal gas conditions), we get:
Ideal step 2 Gas

v2 ,T2 volume

s2
step 1 v1 ,T 1

s=0

s1

Temperature

or in mathematical terms: s s ds = dT + dv = 0 T v v T However, From Equation 5.33:

21

c P ds = v dT + dv T v T To get s1
P= a RT 2 vb v
v 2 P

so

R P = T v v b

and
s1 = ds =
v dv = 2 R dv = R ln v2 b v1 b v1 T v v1 v b

or, using the ideal gas law, we can put s1 in terms of T2:
RT2 b P s1 = R ln 2 v1 b

For step 2
c s 2 = v dT = R T
T1 T2 T2

623.15 K

0.213 + 28.785 10 3 T 8.824 10 6 T 2 dT T

Now add both steps

s = s1 + s 2 = 0 RT2 P b T2 8.824 10 6 2 3 + 0.213 ln ( ) = ln 2 + 28 . 785 10 T 623 . 15 K T2 (623.15 K )2 2 2 v1 b 623.15

Substitute
T1 = 623.15 K

v1 = 600 cm 3 /mol P2 = 1 atm

cm 3 atm R = 82.06 mol K

22

and solve for T2:

T2 = 448.3 [K ]

(b) T, P as independent variables

Choosing T and P as the independent variables, (and changing T under ideal gas conditions), we get:

Pressure

s=0
step 1 step 2 P2,T2

P1,T1

s1

s2

Ideal Gas

Temperature

Mathematically, the entropy is defined as follows

s s ds = dT + dP = 0 P T T P

Using the appropriate relationships, the expression can be rewritten as

c v ds = P dT dP = 0 T T P

For the van der Waals equation

R (v b )

v = T P RT 2a + 2 v3 (v b ) Therefore,

23

s =

T2

T1

cP dT T

P2

2a P1 + 2 v3 (v b ) RT

R (v b )

dP = 0

We cant integrate the second term of the expression as it is, so we need to rewrite dP in terms of the other variables. For the van der Waals equation at constant temperature: 2a RT dP = dv v 3 (v b )2 Substituting this into the entropy expression, we get
1.213 + 28.785 10 3 T 8.824 10 6 T 2 s = dT T
T2 T1 v2 v1

(v b )dv = 0

Upon substituting
T1 = 623.15 K v1 = 600 cm 3 v2 = RT2 (gas acts ideally at 1 atm) P2

cm 3 b = 91 mol cm 3 atm R = 82.06 mol K

we obtain one equation for one unknown. Solving, we get

T2 = 448.3 K

24

5.17 (a) Attractive forces dominate. If we examine the expression for z, we see that at any absolute temperature and pressure, z < 1. The intermolecular attractions cause the molar volume to deviate negatively from ideality and are stronger than the repulsive interactions. (b) Energy balance:
h2 h1 = q

Alternative 1: path through ideal gas state Because the gas is not ideal under these conditions, we have to create a hypothetical path that connects the initial and final states through three steps. One hypothetical path is shown below:
P [bar] P,T1 50 q = h P,T2

step 3 h2 step 2 ideal gas

step 1

h1

h 3

300

500

T [K]

Choosing T and P as the independent properties: h h dh = dT + dP T P P T or using Equation 5.46 v dh = c P dT + T + v dP T P The given EOS can be rewritten as 1 v = R + aT 1 / 2 P

25

Taking the derivative gives:

R v 0.5 = + 0.5aRT T P P

so
dh = cP dT + 0.5aRT 0.5 dP

For step 1
0

h1 =

(0.5aRT1

0.5

50 bar

J )dP = 0.5aRT10.5 P = 252 mol

For step 2
500 K

h2 = R

(3.58 + 3.02 10

300 K

J T 0.875T 0.5 dT = 7961 mol

For step 3:
50 bar

h3 =

(0.5aRT2

0.5

J )dP = 0.5aRT20.5P = 323 mol

Finally summing up the three terms, we get,

J q = h1 + h2 + h3 = 7888 mol
Alternative 2: real heat capacity For a real gas
real h = c P

From Equation 5.48:

real ideal = cP cP

2v T T 2 ideak P
P real

dP P

For the given EOS

26

 1 v = R + aT 1 / 2 P Therefore,
2v = 0.25aRT 1.5 T 2 P

and
2v T T 2 ideak P
P real
real

P =50 bar dP = 0.25aRT 0.5 dP = 0.875 K 1/2 RT 0.5 P P ideak =0 bar

[ ])

real We can combine this result with the expression for c P and find the enthalpy change.

500 K

h = R

(3.58 + 3.02 10

T 0.875T 0.5 dT

300 K

J q = h = 7888 mol

The answers is equivalent to that calculated in alternative 1

27

5.18 (a) Calculate the temperature of the gas using the van der Waals equation. The van der Waals equation is given by:

P=

RT a 2 vb v

First, we need to find the molar volume and pressure of state 1.

m3 V Al 0.1 m 2 (0.4 [m ]) = = 0.00016 v1 = 1 = 250 [mol] n n mol

( [ ])

P1 =

mg + Patm = A

m (10000 [kg]) 9.81 2 0.1 m 2

[ ]

+ 1.01325 10 5 [Pa ] = 1.08 10 6 [Pa ]

Substituting these equations into the van der Waals equation above gives J m3 J 0 .5 8.314 mol K T1 mol 6 1.08 10 [Pa ] = 2 3 3 m 3 5 m m 0.00016 0.00016 4 10 mol mol mol T1 = 297.5 K Since the process is isothermal, the following path can be used to calculate internal energy:
v v2 ,T2 = T 1

u s

v1 ,T1

Thus, we can write the change in internal energy as:

28

 u u u du = dT + dv = dv v T v T T v Using Equation 5.40

v2

u =

v1

T P dv T v

For the van der Waals EOS: P= so R P = T v v b Therefore,

v2

RT a 2 v b v

u =

v1

v 2 dv

We can assume the gas in state 2 is an ideal gas since the final pressure is atmospheric. Therefore, we calculate v 2 , v2 = and J m3 0 . 5 0.0244 mol dv = 3104.5 J u = mol v2 0.00016 or
U = 776.1 [kJ ]

m3 RT2 = 0.0244 P2 mol

29

(b) From the definition of entropy:

suniv = s sys + s surr

First, lets solve for s sys using the thermodynamic web. s s ds sys = dT + dv T v v T Since the process is isothermal, s ds sys = dv v T
P s sys = dv T v v
1

v2

Again, for the van der Waals equation, R P = T v v b Substitution of this expression into the equation for entropy yields
v2

s sys =

v1

v b dv

J 8.314 mol K dv = 44.17 J s sys = 3 mol K 0.00016 v 4 10 5 m mol J S sys = 11042.5 K

0.0244

The change in entropy of the surroundings will be calculated as follows

s surr = Qsurr Tsurr

where
30

Qsurr = Q

(Q is the heat transfer for the system)

Application of the first law provides

Q = U W

We know the change in internal energy from part a, so lets calculate W using
W = n Pdv
v1 v2

Since the external pressure is constant,

m = (250 [mol])( 1.01325 10 5 [Pa ]) 0.0244 m3 0.00016 mol mol
3

W = 614030 [J ]

Now calculate heat transfer.

Q = 776100 [J ] ( )614030 [J ] = 1.39 10 6 [J ]

Therefore,

S surr =

1.39 10 6 [J ] J = 4672 297.5 [K ] K

and the entropy change of the universe is: J J J S univ = 11042.5 4672 = 6370.5 K K K

31

5.19 First, calculate the initial and final pressure of the system.

Pi = 10 10

( 20000 [kg ])(9.81 [m/s 2 ]) [Pa ] + = 4.92 10 6 [Pa ] 2

P f = 10 10

[ ] [Pa ] + (30000 [kg])(9.81 [m/s ]) = 6.89 10 0.05 [m ]

0.05 m
2 2

[Pa ]

To find the final temperature, we can perform an energy balance. Since the system is wellinsulated, all of the work done by adding the third block is converted into internal energy. The energy balance is
u = w

To find the work, we need the initial and final molar volumes, which we can obtain from the given EOS:
vi = 8.37 10 4 m 3 /mol vf = 8.314T f

25 6.89 10 6 1 + Tf

+ 3.2 10 -5 m 3 /mol

Now, calculate the work 8.314T f w = Pf v f vi = 6.89 10 6 Pa + 3.2 10 -5 8.37 10 4 25 6 6 . 89 10 1+ Tf We also need to find an expression for the change in internal energy with only one variable: Tf. To find the change in internal energy, we can create a hypothetical path shown below:

step 2 v step 1 ideal gas

step 3

vi ,Ti u = -P (v -v ) f f i vf ,Tf

500

Tf

32

For step 1, we calculate the change in internal energy as follows

v = RT / Plow

u1 = u1 =

vi

u dv = v T

v = RT / Plow

vi

P P dv T T v

v = RT / Plow

vi

2 2 RTi / Plow b aRTi dv = aRTi ln (T + a )2 (v b ) (T + a )2 v b i i i

Similarly, for step 3:

f P u dv T P dv u3 = = v T T v v = RT / Plow v = RT / Plow

vf

u3 =

aRT 2 dv aRT f 2 vf b f = ln T + a 2 (v b) T + a 2 RT f / Plow b f v = RT / Plow f

vf

Insert the expression for the final molar volume into the equation for u3 :

8.314T f u3 = ln 6 Tf + a 2 6.89 10 1 + 25 / T f RT f / Plow b

aRT f 2

)(

)(

Since the pressure is low (molar volume is big) during the second step, we can use the ideal heat capacity to calculate the change in internal energy.
Tf

u 2 =

Ti = 500 K

cv dT =

Tf

u 2 = 11.686 T f 500 + 0.025 T f2 500 2

Ti = 500 K

(20 R + 0.05T )dT

If we set the sum of the three steps in the internal energy calculation equal to the work and choose an arbitrary value for Plow, 100 Pa for example, we obtain one equation with one unknown:

33

 RTi / Plow b ln + 11.686 T f 500 + 0.025 T f2 500 2 + 2 (Ti + a ) vi b aRTi 2

8.314T f = ln 2 6 Tf + a 6.89 10 1 + 25 / T f RT f / Plow b 8.314T f 6.89 10 6 Pa + 3.2 10 -5 8.37 10 4 25 6 1+ 6.89 10 Tf

aRT f 2

)(

)(

Solving for Tf we get

T f = 536.2 K

The piston-cylinder assembly is well-insulated, so

suniv = s sys

Since the gas in the cylinder is not ideal, we must construct a hypothetical path, such as one shown below, to calculate the change in entropy during this process.

P 6.9 Pf ,Tf

ideal gas Plow 500 step 2 536 T

For steps 1 and 3

s s1 = dP = P T Pi Pi
Plow Plow

v dP T P

34

step 3

4.9

Pi ,Ti step 1

f v s s3 = dP = dP P T T P Plow Plow

Pf

We can differentiate the given EOS as required:

Plow RTi (2a + Ti ) RTi (2a + Ti ) Plow dP = ln s1 = P 2 2 ( ) ( ) a T P a T + + i i i Pi

s3 =

RT 2a + T f f 2 a +Tf P Plow
Pf

) RT f (2a + T f ) P f dP = ln P 2 ( ) a T + low f
Tf

For step 2 c s 20 s 2 = dT = P dT = + 0.05 dT T T P T Ti Ti Ti Tf s2 = 20 ln T + 0.05 T f Ti i

Tf Tf

Sum all of the steps to obtain the change in entropy for the entire process
suniv = s sys = s1 + s 2 + s3 suniv =

RT f 2a + T f Tf Pf RTi (2a + Ti ) Plow + 0.05 T f Ti + ln 20 ln ln P T P 2 (a + Ti )2 + a T i low i f Arbitrarily choose Plow (try 100 Pa), substitute numerical values, and evaluate:

J suniv = 0.388 mol K J J S univ = (2 mol) 0.388 mol K = 0.766 K

35

5.20 A schematic of the process is given by:

well insulated

V=1L T = 500 K nCO=1 mole

V=1L Vacuum

V=2L T=? nCO =1 mole

State i

State f

(a) The following equation was developed in Chapter 5:

real ideal cv = cv +

2P dv T T 2 v v ideal
v

For the van der Waals EOS 2P =0 T 2 Therefore,

real ideal cv = cv

From Appendix A.2: 3100 J real 4 R = 22.0 = R cv 3.376 + 5.57 10 (500) mol K 500 2
(b) As the diaphragm ruptures, the total internal energy of the system remains constant. Because the volume available to the molecules increases, the average distance between molecules also increases. Due to the increase in intermolecular distances, the potential energies increase. Since the total internal energy does not change, the kinetic energy must compensate by decreasing. Therefore, the temperature, which is a manifestation of molecular kinetic energy, decreases.

36

(c) Because the heat capacity is ideal under these circumstances we can create a two-step hypothetical path to connect the initial and final states. One hypothetical path is shown below:
v u 2 s2 vf ,Tf step 2

step 1 u1, s1

vi ,Ti

Tf

500

For the first section of the path, we have

Tf

u1 =

real cv dT

ideal = cv dT Ti

Tf

Ti
Tf

u1 = R

3100 4 2.376 + 5.57 10 T 2 dT T 500 K i 25773.4 u1 = 2.32 10 3 T f2 + (19.75)T f + 10507.4 Tf

For the second step, we can use the following equation

vf

u 2 =

vi

dv v T

If we apply Equation 5.40, we can rewrite the above equation as

vf

u 2 =

P T P dv T v vi RT a 2 , v b v

For the van der Waals EOS, P =

37

R P = T v v b Therefore,
a RT J dv = 73.7 u1 = P dv = 2 v b mol v i = 0.001 v i = 0.001 v Now set the sum of the two internal energies equal to zero and solve for Tf: u1 + u 2 = 2.32 10 3 T f2 + 19.75T f +
T f = 497 K
v f = 0.002 v f = 0.002

25773.4 10507.4 + 73.7 = 0 Tf

(d) Since the system is well-insulated

suniv = s sys

To solve for the change in entropy use the following development: s s ds sys = dT + dv v T T v Using the thermodynamic web, the following relationships can be proven cv s = T v T P s = v T T v For the van der Waals EOS R P = T v (v b ) Now we can combine everything and calculate the change in entropy

38

497 K

s sys =

500 K

cv dT + T

0.002

(v b ) dv 0.001

0.002 497 K 2.376 dv 3100 dT + s sys = R + 5.57 10 4 5 T T3 0.001 v 3.95 10 500 K J suniv = s sys = 5.80 mol K

39

5.21 A schematic of the process is given by:

well insulated

V = 0.1 m3 T = 300 K nA=400 moles

V = 0.1 m3 Vacuum

V = 0.2 m3 T=? nA =400 moles

State i

State f

Energy balance:
u = 0

Because the gas is not ideal under these conditions, we have to create a hypothetical path that connects the initial and final states through three steps. One hypothetical path is shown below:
step 2 v [m 3/mol] step 3 vf ,Tf u 0.1/400 vi ,Ti ideal gas step 1 Tf 300 T [K]

0.2/400

For the first section of the path, we have

v=

u1 =

u dv v T vi

If we apply Equation 5.40, we can rewrite the above equation as

v =

u1 =

P P dv T T v vi

40

For the van der Waals EOS

R a P + = 2 T v v b T v 2
Therefore,
u1 = RT a 2a J P dv = dv = 1120 + 4 v b Tv 2 2 mol vi = 2.510 4 Ti v vi = 2.510
v = v =

Similarly for step 3:

v f = 510 4 v f = 510 4 v =

u3 =

v=

RT a v b + 2 P dv = Tv

2a

Tf v

dv =

168000 J Tf mol K

For step 2, the molar volume is infinite, so we can use the ideal heat capacity given in the problem statement to calculate the change in internal energy:

u 2 =

3 R T f 300 K 2

If we set sum of the changes in internal energy for each step, we obtain one equation for one unknown:
168000 J 3 J u1 + u 2 + u3 = 1120 + T f 300 K + 8.314 =0 Tf mol K mol 2

Solve for Tf:

T f = 261.6 K

41

5.22 A schematic of the process is shown below:

Ethane 3 MPa; 500K

T surr = 293 K Initially: vacuum

(a) Consider the tank as the system. Since kinetic and potential energy effects are negligible, the open system, unsteady-state energy balance (Equation 2.47) is
dU & +W & &in hin n & out hout + Q = n s dt sys in out

The process is adiabatic and no shaft work is done. Furthermore, there is one inlet stream and no outlet stream. The energy balance reduces to
dU &in hin =n dt sys

Integration must now be performed

U2

U1

& dU = n
0

in in

h dt
t

& in dt = nin hin = (n2 n1 )hin n2 u 2 n1u1 = hin n

0

Since the tank is initially a vacuum, n1=0, and the relation reduces to:
u 2 = hin

42

As is typical for problems involving the thermodynamic web, this problem can be solved in several possible ways. To illustrate we present two alternatives below:
Alternative 1: path through ideal gas state Substituting the definition of enthalpy:

u 2 = uin + Pin vin

or
u2 (at 3 MPa, T ) uin (at 3 MPa, 500 K ) = Pin vin

(1)

From the equation of state:

J 8 6 Pin vin = RT (1 + B' P ) = 8.314 mol K (552 K ) 1 2.8 10 3 10 Pa = 3,800

)]

J (2) mol

The change in internal energy can be found from the following path:
P 3 MPa

u1

u3

Plow

u2 step 2 ideal gas 500 K T2 T

For steps 1 and 3, we need to determine how the internal energy changes with pressure at constant temperature: From the fundamental property relation and the appropriate Maxwell relation:

u s v v v = T P = T P P T P T P T T P P T
From the equation of state

RT RT u ' (1 + B'P ) P = 2 = B RT P P T P

43

step 3

step 1

So for step 1:
u u1 = dP = B ' RTdP =B ' RT Pin = 349 [J/mol] P T Pin Pin
0 0

(3)

and for step 3:

u u 3 = dP = B ' RTdP = B ' RT P2 = 0.7T P T 0 0
P2 P2

(4)

For step 2
T T h Pv u u 2 = dT = [c P R ]dT dT = T P T P T P 500 500 500 T

or
u 2 = R
T2

T1 =500 K

[0.131 + 19.225 10

T 5.56110 6 T 2 dT

(5)

Substituting Equations 2, 3, 4, and 5 into 1 and solving for T gives:

T2 = 552 K

Alternative 2: real heat capacity Starting with:

u 2 = hin

The above equation is equivalent to

h2 P2 v2 = hin h2 hin = P2 v2

To calculate the enthalpy difference, we can use the real heat capacity
real ideal cP = cP P 2 v T 2 Pideal T

dP P

For the truncated viral equation,

44

 2v =0 T 2 P

Therefore,
real ideal cP = cP

Now, we can calculate the change in enthalpy and equate it to the flow work term.
T2

T1 = 500 K
T2

cP

ideal

dT = P2 v2
3

T1 =500 K

[1.131 + 19.225 10

T 5.561 10 6 T 2 dT = P2 v2 = RT2 (1 + B' P2 )

Integrate and solve for T2:

T2 = 552 K

(b) In order to solve the problem, we will need to find the final pressure. To do so, first we need to calculate the molar volume. Using the information from Part (a) and the truncated virial equation to do this
J (552 K ) 8.314 mol K 3 10 Pa
6

v=

RT (1 + B' P ) = P

[1 2.8 10 (3 10 Pa )]
8 6

m3 v = 0.0014 mol

This quantity will not change as the tank cools, so now we can calculate the final pressure.
m3 P2 0.0014 mol = 1 2.8 10 8 P2 J (293 K ) 8.314 mol K

Solve for P2 :
45

P2 = 1.66 10 6 Pa

The entropy change of the universe can be expressed as follows:

S univ = S sys + S surr

To solve for the change in entropy of the system start with the following relationship:
s s ds sys = dT + dP T P P T

Alternative 1: path through ideal gas state Using the proper relationships, the above equation can be rewritten as
ds sys = cP v dT + dP T T P

We can then use the following solution path:

P 3 MPa

1.66 MPa step 1 s 1 s 2 step 2 ideal gas 500 K

Plow

step 3 T

s3

T2

Choosing a value of 1 Pa for Plow, for step 1:

R v ' s1 = dP = (1 + B P )dP T P P 1.66 MPa 1.66 MPa
1 Pa 1 Pa

For step 3,
3 MPa

s1 =

1 Pa

v dP = T P

3 MPa

1 Pa

R 1 + B ' P dP P

46

For step 2:
s 2 =
293 K cP 1.131 dT R = + 19.225 10 3 5.561 10 6 T dT T T 552 K 552 K 293 K

Adding together steps 1, 2 and 3:

J s sys = 46.9 mol K ______________________________________________________________________________
Alternative 2: real heat capacity Using the proper relationships, the above equation can be rewritten as
c real v ds sys = P dT + dP T T P

For the truncated virial equation

v 1 = R + B ' T P P

Now, substitute the proper values into the expression for entropy and integrate:
1.6610 6 Pa

293 K

s sys = R

552 K

1.131 + 19.225 10 3 5.561 10 6 T dT + R T

1 + B' dP P 310 ^ Pa

J s sys = 46.9 mol K ______________________________________________________________________________

In order to calculate the change in entropy of the surroundings, first perform an energy balance.
u = q

Rewrite the above equation as follows

h (Pv ) = q

47

Since the real heat capacity is equal to ideal heat capacity and the molar volume does not change, we obtain the following equation
Tf Ti T f = 293K

cP

ideal

dT v P f Pi = q

Ti = 552 K

[1.131 + 19.225 10

m3 6 6 T 5.561 10 6 T 2 dT 0.0014 1.66 10 Pa - 3 10 Pa = q mol

J q = 15845 mol

Therefore,
J q surr = 15845 mol

and
J s surr = 54.08 mol K

Before combining the two entropies to obtain the entropy change of the universe, find the number of moles in the tank.
n= 0.05 m 3 = 75.7 mol m3 0.0014 mol

[ ]

Now, calculate the entropy change of the universe.

J J S univ = (75.7 mol) 54.08 mol K + 46.9 mol K J S univ = 544 K

48

5.23 First, focus on the numerator of the second term of the expression given in the problem statement. We can rewrite the numerator as follows:
ideal ideal ideal ideal uT r , v r uT = uT r , v r uT uT uT r ,vr r ,vr = r ,vr r ,vr =

)(

For an ideal gas, we know

ideal ideal uT uT =0 r ,vr r ,vr =

Therefore,
ideal ideal uTr , v r uT = uTr , v r uT ,vr ,vr = r r

Substitute this relationship into the expression given in the problem statement:
dep uT ,v
r

RTc

ideal ideal uTr , v r uT uTr , v r uT ,vr ,vr = r r = = RTc RTc

ideal Now, we need to find an expression for uTr , vr uT . Note that the temperature is constant. r ,vr = Equation 5.41 reduces to the following at constant temperature:

P duT = T P dv T v

The pressure can be written as

P= zRT v

and substituted into the expression for the differential internal energy
RT z RT 2 z RT zRT + = duT = T dv dv v T v v v T v v v

Applying the Principle of Corresponding States

49

duTr

T 2 z = r T RTc vr r

dvr vr

If we integrate the above expression, we obtain

ideal vr 2 uT r , v r u T T z r, vv = = r RTc = RTc Tr vr vr v= v = v

duTr

dv r

Therefore,
dep uT ,v
r

RTc

ideal ideal vr 2 uT r , v r u T u T r , v r uT T z v , ,vr = r r r = = = r Tr RTc RTc vr vr v=

dv r

50

5.24 We write enthalpy in terms of the independent variables T and v:

h h dh = dT + dv T v v T

using the fundamental property relation:

dh = Tds + vdP

At constant temperature, we get:

P P dhT = T + v dv v T T v

For the Redlich-Kwong EOS 1 R a P + = 3 / 2 T v v b 2 T v(v + b )

RT a a P + + = v T (v b )2 T 1 / 2 v 2 (v + b ) T 1 / 2 v(v + b )2

Therefore,
RT 3 RTv a a + + dhT = dv 2 1/ 2 2 1/ 2 2 v b ( ) + T v v b ( ) ( ) + v b T v b

To find the enthalpy departure function, we can integrate as follows

h
dep

v =

dhT =

RT RTv a a 3 dv + + v b (v b )2 2 T 1 / 2 v(v + b ) T 1 / 2 (v + b )2 v=
v

Since temperature is constant, we obtain

h dep =

3a RTb a v + + ln v b 2bT 1 / 2 v + b T 1 / 2 (v + b )

To calculate the entropy departure we need to be careful. From Equation 5.64, we have:
ideal gas ideal gas ideal gas ideal gas sT , P sT = sT , P sT sT ,P , P = 0 sT , P , P =0

)(

51

However, since we have a P explicit equation of state, we want to put this equation in terms of v. Lets look at converting each state. The first two states are straight -forward
sT , P = sT , v

and
ideal gas ideal gas sT , P = 0 = sT , v =

For the third state, however, we must realize that the ideal gas volume v at the T and P of the system is different from the volume of the system, v. In order to see this we can compare the equation of state for an ideal gas at T and P
P= RT v'

to a real gas at T and P

P= RT a vb T v(v + b )

The volume calculated by the ideal gas equation, v, is clearly different from the volume, v, calculated by the Redlich-Kwong equation. Hence:
ideal gas gas ideal gas ideal gas ideal gas sT = s ideal = sT +s ' sT ,P ,v ,v , T ,v ' T v

Thus,
ideal gas ideal gas ideal gas ideal gas ideal gas ideal gas = sT , v sT sT sT sT , P sT s ' ,P , v = sT , v ,v = ,v T ,v

)(

Using a Maxwell relation:

ds P = dv T T v

Therefore,
P dsT = dv T v

52

For the Redlich-Kwong EOS 1 R a P + = 3 / 2 T v v b 2 T v(v + b ) so

(s

ideal gas T , v sT , v = =

a 1 + dv 3/ 2 2 v b ( ) + T v v b v =

v R

For an ideal gas

R P = T v v

so

(
Finally:

ideal gas ideal gas sT sT ,v ,v = =

R dv v v=

gas s ideal ' T ,v

ideal gas sT ,v

dv v' RT = R = R ln = R ln v v Pv
v

v'

Integrating and adding together the three terms gives: s dep = R ln

(v b ) +
v

RT v ln R ln Pv 2bT 3 / 2 v + b a

53

5.25 Calculate the reduced temperature and pressure:

Tc = 647.3 [K ] w = 0.344

Pc = 220.48 [bar ]

(Table A.1.2)

300 [bar ] = 1.36 220.48 [bar ] 673.15 K Tr = = 1.04 647.3 K Pr = By double interpolation of data from Tables C.3 and C.4

h dep Tr , Pr RTc

( 0)

= 2.921

h dep Tr , Pr RTc

(1)

= 1.459

From Tables C.5 and C.6:

s dep Tr , Pr R
( 0)

= 2.292

s dep Tr , Pr R

(1)

= 1.405

Now we can calculate the departure functions

dep hTr , Pr h dep = RTc RTc
( 0)

h dep Tr , Pr + w RTc

(1)

J J h dep = 8.314 mol K (647.3 )( 2.921 + 0.344( 1.459)) = 18421 mol dep sTr , Pr s dep = R R
( 0)

s dep Tr , Pr + w R

(1)

J J s dep = 8.314 mol K ( 2.292 + 0.344( 1.405)) = 23.07 mol K

54

To use the steam tables for calculating the departure functions, we can use the following relationships.
ideal h dep = hT , P hT ,P ideal s dep = sT , P sT ,P

From the steam tables

kJ kJ hT , P = 2151.0 and sT , P = 4.4728 kg kg K

We need to calculate the ideal enthalpies and entropies using the steam tables reference state.
ideal vap (0 .01 C ) + hT , P = h 673.15 K c ideal dT p 273.16 K

kJ from the steam tables and heat capacity data from Table A.2.2. We can get h vap = 45.1 mol Using this information, we obtain
kJ kJ ideal 0.008314 hT + , P = 45.1 mol mol K
3.47 + 1.45 10 273.16 K
673.15 K
3

0.121 10 5 T+ dT T2

kJ ideal hT , P = 59.14 mol

Now, calculate the ideal entropy.

ideal vap (0 .01 C) + sT , P = s 673.15 K c ideal p

273.16 K

P2 dT R ln P 1

From the steam tables:

kJ s vap (0.01 C ) = 0.165 mol K

Substitute values into the entropy expression:

55

 ideal sT , P = 0.165 + 0.008314

J ideal sT , P = 107 mol K

673.15 K 5 kJ 3.47 30 3 0.121 10 dT + + 1 . 45 10 ln T 3 0 . 000613 mol K T 273.16 K

Now, calculate the departure functions:

kJ kJ kJ h dep = 2151.0 (0.0180148 [kg/mol]) 59.14 = 20.4 mol mol kg kJ kJ kJ (0.0180148 [kg/mol]) 0.107 s dep = 4.4728 = 0.0264 mol K mol K kg K

Table of Results Generalized Percent Difference Steam Tables Tables (Based on steam tables)
kJ h dep mol kJ s dep mol K

-18.62 -0.0231

-20.4 -0.0264

9.9 12.5

56

5.26 State 1 is at 300 K and 30 bar. State 2 is at 400 K and 50 bar. The reduced temperature and pressures are

30 [bar ] = 0.616 48.74 [bar ] 300 K T1, r = = 0.982 305.4 K

P 1, r =

50 [bar ] = 1.026 48.74 [bar ] 400 K T2,r = = 1.31 305.4 K

P2,r =

and

= 0.099
By double interpolation of data in Tables C.3 and C.4
h dep T1, r , P1, r RT c h dep T2 , r , P2 , r RT c
( 0)

= 0.825

h dep T1, r , P1, r RT c h dep T2 , r , P2 , r RT c

(1)

= 0.799

( 0)

= 0.711

(1)

= 0.196

Therefore,
h dep T1, r , P1, r RT = 0.825 + 0.099( 0.799 ) = 0.904 c h dep T2 ,r , P2 ,r = 0.711 + 0.099( 0.196) = 0.730 RTc

The ideal enthalpy change from 300 K to 400 K can be calculated using ideal cP data from Table A.2.1.
400 K ideal hT =R T
1 2

1.131 + 19.225 10

T 5.56110 6T 2 dT = 717.39 R

300 K

The total entropy change is

57

ideal h = hT , P + hT + hT , P T2 1, r 1, r 1 2,r 2,r h = R[ ( )0.904TC + 717.39 0.730TC ]

dep

dep

J h = 8.314 mol K [0.904(305.4 K ) + 717.39 K 0.730(305.4 K )] J h = 6406.2 mol

Using the data in Table C.5 and C.6

s dep T1, r , P1, r R s dep T2 , r , P2 , r R = 0.601 + 0.099( 0.756 ) = 0.676 = 0.394 + 0.099( 0.224 ) = 0.416

Substituting heat capacity data into Equation 3.62, we get

400 K 1.131 + 19.225 10 3 T 5.561 10 6 T 2 50 bar dT ln s ideal = R 30 bar T 300 K s ideal = 1.542 R

Therefore,
s = sT , P + s ideal + sT , P = R(0.676 + 1.542 0.416 ) 1, r 1, r 2,r 2,r
dep dep

J s = 14.98 mol K

58

5.27 The turbine is isentropic. Therefore, we know the following

s = sT , P + s ideal + sT , P = 0 1, r 1, r 2,r 2,r

dep

dep

Using the van der Waals EOS, we can find P1,r, which leaves one unknown in the above equation: T2.
3 82.06 cm atm (623.15 K ) mol K 3 3 600 cm 91 cm mol mol atm cm 3 91 10 5 mol 2 3 600 cm mol
2

P1 =

P1 = 75.19 [atm] = 76.19 [bar ]

Calculate reduced temperature and pressures using data from Table A.1.1 76.19 [bar ] = 1.8 42.44 [bar ] 623.15 K T1, r = = 1.68 370.0 K
P 1, r = P2,r =

1.013 [bar ] = 0.024 42.44 [bar ]

Also,

= 0.152
From Tables C.5 and C.6:
s dep T1, r , P1, r R = 0.327 + 0.152( 0.102 ) = 0.343

Substituting heat capacity data into Equation 3.62, we get

s
ideal

T2 1.213 + 28.785 10 3 T 8.824 10 6 T 2 1 atm =R dT ln 75.19 atm T 623.15 K

Therefore,

59

 s dep T2 1.213 + 28.785 10 3 T 8.824 10 6 T 2 T2 , r , P2 , r R 0.343 + dT + 4 . 32 + T R 623.15 K We can solve this using a guess-and-check method
T2 = 600 K : T2,r = 1.62

= s

J s = 33.84 mol K
T2 = 450 K : T2,r = 1.22

J s = 0.77 mol K
T2 = 446.6 K : T2,r = 1.21

J s 0 mol K Therefore,
T2 = 446.6 K

60

5.28 A reversible process requires the minimum amount of work. Since the process is reversible and adiabatic
s = 0

which can be rewritten as s = sT , P + s ideal + sT , P = 0 1, r 1, r 2,r 2,r Calculate reduced temperature and pressures using data from Table A.1.1 1 [bar ] = 0.0217 46.0 [bar ] 300 K T1, r = = 1.57 190.6 K P 1, r = From Tables C.5 and C.6:
s dep T1, r , P1, r R = 0.00457 + 0.008( 0.0028) = 0.0046
dep dep

P2,r =

10 [bar ] = 0.217 46.0 [bar ]

Substituting heat capacity data into Equation 3.62, we get s

ideal

T2 1.702 + 9.081 103T 2.164 106 T 2 10 bar = R dT ln T 300 K 1 bar

Therefore, s dep T2 3 6 2 + T T 1 . 213 28 . 785 10 8 . 824 10 T2 , r , P2 , r s = R 0.0046 + dT 2.303 + T R 300 K We can solve using a guess-and-check method
T2 = 400 K : T2,r = 2.10 J s = 4.98 mol K T2 = 385 K :

T2,r = 2.02

61

 J s = 1.42 mol K
T2 = 379 K :

T2,r = 1.99 J s = 0.018 mol K

Therefore,
T2 379 K

An energy balance reveals that h2 h1 = h = ws We can calculate the enthalpy using departure functions. From Tables C.3 and C.4:
h dep T1, r , P1, r RT = 0.0965 + 0.008( 0.011) = 0.0966 c dep h T2 , r , P2 , r RT = 0.0614 + 0.0089(0.015) = 0.0613 c

Ideal heat capacity data can be used to determine the ideal change in enthalpy 379 K h ideal = R 1.702 + 9.081 10 3 T 2.164 10 6 T 2 dT 300 K Therefore,
379 K J 3 6 2 ( )( ) 8 . 314 190 . 6 K 0 . 0966 0 . 0613 1 . 702 9 . 081 10 T 2 . 164 10 T dT h = + + mol K 300 K

J & s = h = 3034.2 w mol and mol J & = W S 1 / 30 s 3034.2 mol = 101.1 W

62

5.29 Equation 4.71 states

1 v = v T P v v = T P This can be substituted into Equation 5.75 to give

JT =

v(T 1) cP

63

5.30 For an ideal gas

R v = T P P Therefore, RT v P = (v v ) = 0 JT = cP cP This result could also be reasoned from a physical argument.

64

5.31 The van der Waals equation is given by:

P=

RT a v b v2

(1)

The thermal expansion coefficient is given by:

1 v 1 T = v T P v v P

(2)

Solving Equation 1 for T: a v b T = P + 2 v R Differentiating by applying the chain rule, a 1 v b 2a Pv 3 av + 2ab T P = + = v P v 2 R R v3 Rv 3 Substitution into Equation 2 gives (3)

Rv 2 Pv 3 av + 2ab

Substituting Equation 1 for P gives b in terms of R, T, v, a , and b:

Rv 2 (v b ) 2 RTv 3 2a(v b )

The isothermal compressibility is given by:

1 v 1 P = v P T v v T

From the van der Waals equation: RT 2a RTv 3 + 2a(v b ) P + = = 2 (v b )2 v 3 v 3 (v b ) v T so

2

65

v 2 (v b ) 2 RTv 3 2a(v b )
2

For the Joule-Thomson coefficient, we can use Equation 5.75:

v T v T P Preal 2 v T T 2 dP P Pideal

JT =
ideal cP

Substituting the van der Waals equation into Equation 3 gives RTv 3 2a(v b ) T 2a(v b ) T = = 3 (v b )Rv (v b ) Rv 3 v P
2

(4)

Thus, the second derivative becomes:

2T 1 T 2a 6a(v b ) T v 2 = (v b )2 + v b v Rv 3 + Rv 4 P P

or simplifying using Equation 4,

2T 2a (v 3b ) v 2 = Rv 4 P

(5)

Substituting Equations 5 and 4 into Equation 5.75 gives: bRTv 3 + 2av(v b ) 2 RTv 3 2a(v b ) = Preal RTv 4 ideal dP cP 2a(v 3b ) Pideal
2

JT

At a given temperature the integral in pressure can be rewritten in terms of volume using the van der Waals equation to give:

66

 JT =
ideal cP

bRTv 3 + 2av(v b ) 2 RTv 3 2a(v b ) vreal RTv RTv 3 2a(v b )2 dv + 2a(v 3b ) (v b )2 videal
2

67

5.32 We can solve this problem by using the form of the Joule-Thomson coefficient given in Equation 5.75. The following approximation can be made

v v T P T P At 300 C, (350 C,1MPa ) v (250 C,1MPa ) v v = 350 250 C T P

m3 m3 0.28247 0.23268 kg kg v = 350 250 C T P m3 m3 v = 0.0005 = 0.0005 kg C kg K T P

A similar process was followed to find cP.

h h P = c dT P T P

At 300 C,
(350 C,1MPa ) h (250 C,1MPa ) h h = T 350 250 C P

h T P h h = 2.15 kJ = 2.15 kJ P = c dT T kg C kg K P P Now, JT can be found.

kJ kJ 3157.7 2942.6 kg kg = 350 250 C

68

3 3 v (573.15 K ) 0.0005 m 0.25794 m T v T kg kg K P = JT = P c kJ 2.15 kg K

JT = 0.0133

m3 K kJ

69

5.33 At the inversion line, the Joule-Thomson coefficient is zero. From Equation 5.75:
v T v T P =0 Preal 2 v T dP 2 T P Pideal

JT =
ideal cP

This is true when the numerator is zero, i.e., v T v = 0 T P For the van der Waals equation, we have P= RT a 2 v b v

Solving for T: a v b T = P + 2 v R so a 1 v b 2a Pv 3 av + 2ab T = = P + 2 v R R v3 Rv 3 v P Substituting for P: RTv 3 2a(v b ) T = (v b )Rv 3 v P Hence, bRTv 3 + 2av(v b ) v T v = 0 = 2 RTv 3 2a(v b ) T P Solving for T: T= 2av(v b ) bRv 3
2 2 2

(1)

70

Substituting this value of T back into the van der Waals equation gives 2av(v b ) a a(2v 3b ) 2 = bv 3 v bv 2

P=

(2)

We can solve Equations 1 and 2 by picking a value of v and solving for T and P. For N2, the critical temperature and pressure are given by Tc = 126.2 [K] and Pc = 33.84 [bar], respectively. Thus, we can find the van der Waals constants a and b:
RT Jm 3 a = 27 c = 0.137 2 64 Pc mol 2

b=

m3 RTc = 3.88 10 -5 8 Pc mol

Using these values in Equations (1) and (2), we get the following plot:
Joule-Thomson inversion line 1000

800

600

400

200

0 0 100 200 T [K] 300 400

71

5.34 We can solve this problem using departure functions, so first find the reduced temperatures and pressures.

50 [bar ] = 0.99 50.36 [bar ] 273.15 K T1, r = = 0.967 282.4 K P 1, r =

P2,r =

10 [bar ] = 0.2 50.36 [bar ]

Since the ethylene is in two-phase equilibrium when it leaves the throttling device, the temperature is constrained. From the vapor-liquid dome in Figure 5.5:
T2,r 0.76 T2 = 214.6

The process is isenthalpic, so the following expression holds

ideal h = hT , P + hT + hT , P = 0 T2 1, r 1, r 1 2,r 2,r dep dep

Therefore,
ideal hT , P = hT , P hT T2 2,r 2,r 1, r 1, r 1 dep dep

From Table A.2.1:

214.6 K
ideal hT 1 T2

=R

[1.424 + 14.394 10

T 4.392 10 6 T 2 dT

273.15 K

From Tables C.3 and C.4 ( = 0.085) :

h dep T1,r , P1,r RT c = 3.678 + 0.085( 3.51) = 3.976

Now we can solve for the enthalpy departure at state 2.

72

dep hT ,P
2,r

2,r

RTc
dep hT ,P
2,r 2,r

214.6 K 1 3 6 2 1 . 424 14 . 394 10 T 4 . 392 10 T dT = 3.976 + 282.4 K 273.15 K

RTc

= 3.01

We can calculate the quality of the water using the following relation
dep hT ,P
2,r

2,r

RTc

= (1 x )

dep, liq hT ,P
2,r

2,r

RTc

+x

dep, vap hT ,P
2,r 2,r

RTc

where x represents the quality. From Figures 5.5 and 5.6:

dep, liq hT ,P
2,r

2,r

RTc
dep, vap hT ,P
2,r 2,r

= 4.6 + 0.085( 5.5) = 5.068 = 0.4 + 0.0859( 0.75) = 0.464

RTc Thus,
x = 0.447

55.3% of the inlet stream is liquefied.

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5.35 Density is calculated from molar volume as follows:

MW v

2 Substitute the above into the expression for Vsound :

P 2 Vsound = MW v

P = 1 MW (1 / v ) s s

The following can be shown using differentials:

v 1 = v v2

Therefore, P v 2 P 2 Vsound = = MW v s s

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5.36 From Problem 5.35:

2 Vsound

P v 2 P = = MW v s s

The thermodynamic web gives: P s T P T s P s P = = = v s s v v P v s T s s v v T s T T P

T P = c v s v cP s P c P = c v v T s T T P T T v v P

If we treat air as an ideal gas consisting of diatomic molecules only

cP 7 = cv 5

R P = T v v

P T = v P R

Therefore, P 7 P = v s 5 v and
Vsound = v 2 7 P = MW 5 v 7 RT 5 MW

Vsound = 343 [m/s]

The lightening bolt is 1360 m away.

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5.37 From Problem 5.35:

2 Vsound

P v 2 P = = MW v s s

The thermodynamic web gives: P s T P T s P s P = = = v s s v v P v s T s s v v T s T T P so

T P T c P P = c v s v T v v P T

For liquids c P cv water at 20 C, so P P T = v s T v v P However, the cyclic rule gives: P T v 1 = T v v P P T So P P = v s v T From the steam tables, for saturated water at 20 oC: m3 = . 001002 P = 2.34 kPa and v kg For subcooled water at 20 oC:

= . 0009995 P = 5 MPa and v

m3 kg
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So kg kPa 5000 2.34 P P P = = s v T v .0009995 .001002 v m3 and P 2 = 1414 [m/s] Vsound = v s v

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5.38 (a) The fundamental property relation for internal energy is

dU = Qrev + Wrev Substituting the proper relationships for work and heat, we obtain
dU = TdS + Fdz

The fundamental property relation for the Helmholtz energy is

dA = dU d (TS ) = dU TdS SdT

Substitute the expression for the internal energy differential:

dA = Fdz SdT

(b) First, relate the entropy differential to temperature and length.

S S dS = dT + dz T z Z T

Now we need to find expressions for the partial derivatives. u TS + Fz S nc z = n = = T T T z z T z Therefore, nc S a = z = n + b T T z T The following statement is true mathematically (order of differentiation does not matter): Z A A = T z T T Z T z

Furthermore,

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 Z T

A S = Z T T z T A F = Z T z T z

S F = = k (z z0 ) Z T T z

Substituting the expressions for the partial derivatives into the expression for the entropy differential, we obtain a dS = n + b dT k (z z 0 )dz T
(c) First, start with an expression for the internal energy differential:

U U dU = dT + dz T z Z T From information given in the problem statement: U = n(a + bT ) T z Using the expression for internal energy developed in Part (a) and information from Part (b) U S = T + F = T ( k ( z z 0 )) + kT ( z z 0 ) = 0 Z T z T Therefore,
dU = [n(a + bT )]dT + 0dz = [n(a + bT )]dT

(d) We showed in Part (c) that

U FU = =0 z T

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 S Using the expression for developed in Part B, we obtain z T S FS = T = kT ( z z0 ) z T

(e) First, perform an energy balance for the adiabatic process.
dU = W

Substitute expressions for internal energy and work.

[n(a + bT )]dT = Fdz = kT (z z 0 )dz

Rearrangement gives dT kT ( z z 0 ) = dz [n(a + bT )] The right-hand side of the above equation is always positive, so the temperature increases as the rubber is stretched.

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5.39 The second law states that for a process to be possible,

suniv 0 To see if this condition is satisfied, we must add the entropy change of the system to the entropy change of the surroundings. For this isothermal process, the entropy change can be written
ds = cv P P dT + dv = dv T T v T v

Applying the van der Waals equation: ds = Integrating

s sys = R ln v2 J = 11.5 v1 mol K

R dv v b

For the entropy change of the surroundings, we use the value of heat given in Example 5.2: J q = q surr = 600 mol Hence the entropy change of the surroundings is:
s surr = q surr 600 J = = 1.6 373 Tsurr mol K

and J suniv = s sys + ssurr = 9.9 mol K Since the entropy change of the universe is positive we say this process is possible and that it is irreversible. Under these conditions propane exhibits attractive intermolecular forces (dispersion). The closer they are together, on average, the lower the energy. That we need to put work into this system says that the work needed to separate the propane molecules is greater than the work we get out during the irreversible expansion.

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5.40 A schematic of the process is given by:

Gas A in Pi = 100 bar Ti = 600 K

Turbine
Gas A out

ws Pf = 20 bar Tf = 445 K

The energy balance for this process is provided below: h = wS Because the gas is not ideal under these conditions, we have to create a hypothetical path that connects the initial and final states through three steps. One hypothetical path is shown below:
100 ideal gas P [bar] step 1 Pi ,Ti

h Pf ,Tf 20 step 3 step 2

Plow

445

600

T [K]

For the first section of the path, we have

P =0

h1 =

h dP P T P1

If we apply Equation 5.45 we can rewrite the above equation as

P =0

h1 =

v + v dP Ti T P Pi

For the given EOS:

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R aP v = 2 T P P Ti

Therefore, 2aP aP J = + P v dP b dP = 2467 h1 = + + 5 Ti T mol Pi =10010 Pi =10010 5 i Similarly for step 3

Pf = 2010 5 P =0 v =0

h3 =

P =0

2aP J + b dP = 250 Tf mol

For step 2, the pressure is zero, so we can use the ideal heat capacity given in the problem statement to calculate the enthalpy change.
Tf

h2 =

Ti

c P dT = (30 + 0.02T )dT = 6270 mol

600 K

445 K

Now sum each part to find the total change in enthalpy: J h = h1 + h2 + h3 = 8487 mol J ws = 8487 mol In other words, for every mole of gas that flows through the turbine, 8487 joules of work are produced.

83