Engineering and Chemical Thermodynamics: Chapter 3 Solutions

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 = δq
cv dT = δq
Using the definition of entropy,
δq rev
final T2
cv dT
∆s sys ,step1 = ∫
initial
T
= ∫ 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 = −δw
For an ideal gas, the following can be shown
RT
δwrev = − Pdv = − dv
v
Therefore,
δqrev ⎛ v2 ⎞
final v2
R
∆s sys ,step 2 = ∫
initial
T
= ∫ v dv = R ln⎜⎜⎝ v
v1
⎟⎟
1 ⎠
Combination of both steps yields
T2
cv dT ⎛v ⎞
∆s sys = ∫ T
+ R ln⎜⎜ 2 ⎟⎟
⎝ v1 ⎠
T1
2
3.2
Equation 3.62 states
T2
cP ⎛P ⎞
∆s sys = ∫T dT − R ln⎜⎜ 2 ⎟⎟
⎝ P1 ⎠
T1
Substituting the equation for c P yields
T2
A + BT + CT 2 ⎛P ⎞
∆s sys = ∫ T
dT − R ln⎜⎜ 2 ⎟⎟
⎝ P1 ⎠
T1
⎛T ⎞
( )⎛P ⎞
∆s sys = A ln⎜⎜ 2 ⎟⎟ + B(T2 − T1 ) + T22 − T12 − R ln⎜⎜ 2 ⎟⎟
C
⎝ T1 ⎠ 2 ⎝ P1 ⎠
3
3.3
Equation 3.3 states
∆S univ = ∆S sys + ∆S surr
where
∆S sys = m( sˆ2 − sˆ1 )

Qsurr
∆S surr = (the temperature of the surroundings is constant)
Tsurr
First, we will calculate ∆S sys . From the steam tables:
⎡ kJ ⎤
sˆ1 = 7.1228 ⎢ ⎥ (300 ºC, 10 bar)
⎣ kg ⋅ K ⎦
Since the container is rigid and mass is conserved in the process,
vˆ2 = vˆ1
⎡ m3 ⎤
vˆ1 = 0.25794 ⎢ ⎥ (300 ºC, 10 bar)
⎣⎢ kg ⎦⎥
⎡ m3 ⎤
∴ vˆ2 = 0.25794 ⎢ ⎥
⎢⎣ kg ⎥⎦
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 ⎤
vˆ2l , sat = 0.001043 ⎢ ⎥ (sat. H2O(l) at 1 bar)
⎣⎢ kg ⎦⎥
⎡ m3 ⎤
vˆ2v, sat = 1.6940 ⎢ ⎥ (sat. H2O(v) at 1 bar)
⎢⎣ kg ⎥⎦
Since vˆ2l , sat < vˆ2 < vˆ2v, sat , two phases are present. The quality of the water can be calculated as
follows
vˆ2 = (1 − x )vˆ2l , sat + xvˆ2v, sat
Therefore,
4
x = 0.152
From the steam tables:
⎡ kJ ⎤
sˆ2l , sat = 1.3025 ⎢ ⎥ (sat. H2O(l) at 1 bar)
⎣ kg ⋅ K ⎦
⎡ kJ ⎤
sˆ2v, sat = 7.3593 ⎢ ⎥ (sat. H2O(v) at 1 bar)
⎣ kg ⋅ K ⎦
The entropy of state 2 can be calculated using the following equation:
sˆ2 = (1 − x )sˆ2l , sat + xsˆ2v, sat

⎡ kJ ⎤
sˆ2 = 2.2231 ⎢ ⎥
⎣ kg ⋅ K ⎦
Now the entropy change of the system can be calculated.
⎛ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞
∆S sys = (10 [kg ])⎜⎜ 2.2231 ⎢ ⎟ = −49.0 ⎡ ⎤
kJ
⎥ − 7.1228 ⎢ ⎥ ⎟ ⎢ ⎥
⎝ ⎣ kg ⋅ K ⎦ ⎣ kg ⋅ K ⎦ ⎠ ⎣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:
[( ) ]
∆U = m (1 − x )uˆ 2l , sat + xu 2v, sat − uˆ1
From the steam tables
⎡ kJ ⎤
uˆ1 = 2793.2 ⎢ ⎥ (300 ºC, 10 bar)
⎣ kg ⎦
⎡ kJ ⎤
uˆ 2l , sat = 417.33 ⎢ ⎥ (sat. H2O(l) at 1 bar)
⎣ kg ⎦
5
⎡ kJ ⎤
uˆ 2v, sat = 2506.1 ⎢ ⎥ (sat. H2O(v) at 1 bar)
⎣ kg ⎦
The expression for internal energy yields
∆U = −20583.77 [kJ ]
Therefore,
Q = −20583.77 [kJ ]
and
Qsurr 20583.77 [kJ ] ⎡ kJ ⎤

∆S surr = = = 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.
6
3.4
Entropy Balance:
Considering the copper block to be the system, no work is done on the system; thus, the energy
balance is
du = δq (neglecting PE and KE)

cv dT = δq
This can be used in the following expression for entropy
T2
δq rev
∆s sys = ∫ T
T1
T2
cv
∆s sys = ∫T dT
T1
From Table A.2.3
c P = 2.723R
cv = c P = 2.723R (for liquids and solids)
Therefore,
⎡ J ⎤ ⎞ ⎛ 280 [K ] ⎞
T2
2.723R ⎛T ⎞ ⎛
∆s sys = ∫ T
dT = 2.723R ln⎜⎜ 2 ⎟⎟ = 2.723⎜⎜ 8.314 ⎢
⎝ T1 ⎠ ⎝
⎟⎟ ln⎜⎜ ⎟⎟
⎣ mol ⋅ K ⎥⎦ ⎠ ⎝ 373.15 [K ] ⎠
T1
⎡ J ⎤
∆s sys = −6.50 ⎢
⎣ mol ⋅ K ⎥⎦
⎛ ⎞
⎜ ⎟
⎜ 10 [kg ] ⎟⎛⎜ − 6.50 ⎡ J ⎤ ⎞⎟ = −1024 ⎡ J ⎤
∆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
Qsurr −Q − nCu c P (T2 − T1 ) − 2.723nCu R(T2 − T1 )

∆S surr = = = =
Tsurr Tsurr Tsurr Tsurr
7
⎛ ⎞⎛⎜ ⎛ ⎡ J ⎤⎞ ⎞
⎜ ⎟ 2.723⎜⎜ 8.314 ⎢ ⎥ ⎟⎟(280 [K ] − 373.15 [K ]) ⎟
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 ⎦
8
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 ⎢ ⎟⎟
δqrev − n ∆h ⎣ mol ⎥⎦ ⎠
liquid
⎡J⎤
vap
⎝
∆S sys = n ∫
vapor
T
=
Tb
=
111 K
= −73.9 ⎢ ⎥
⎣K ⎦
The sign is negative because there is less randomness in the liquid phase.
(c)
For this situation
δq = c P dT
Therefore,
δq rev ⎛ ⎡ J ⎤ ⎞ ⎛ 273.15 K ⎞
Tf 273.15 K
∆S sys = m ∫ = ∫
cP
dT = (18.0148 g )⎜
⎜ 4.2 ⎢ g ⋅ K ⎥ ⎟⎟ ln⎜ 373.15 K ⎟
Ti
T 373.15 K
T ⎝ ⎣ ⎦⎠ ⎝ ⎠
⎡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:
9
∆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
⎡ ⎛T ⎞ ⎛ P ⎞⎤
∆S sys = n ⎢c P ln⎜⎜ 2 ⎟⎟ − R ln⎜⎜ 2 ⎟⎟⎥
⎣ ⎝ T1 ⎠ ⎝ P1 ⎠⎦
From the problem statement, we know
P1 = 2 [bar ]
P2 = 1 [bar ]
The ideal gas law can be used to solve T1 .
PV
T1 = 1 1 =
(2 [bar ])(10 L ) = 240.6 [K ]
nR ⎛ ⎡ L ⋅ bar ⎤ ⎞
⎜⎜ 0.08314 ⎢ ⎟⎟(1 [mol])
⎝ ⎣ mol ⋅ K ⎥⎦ ⎠
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
T2 V2
n ∫ cv dT = − ∫ PE dV
T1 V1
11
Since cv and PE are constant
ncv (T2 − T1 ) = − PE (V2 − V1 )
V2 and T1 can be rewritten using the ideal gas law
nRT2
V2 =
P2
PV
T1 = 1 1
nR
Substituting these expressions into the energy balance, realizing that PE = P2 , and simplifying
the equation gives
⎛ 5 ⎞
⎜ P2 + P1 ⎟V1
T2 = ⎝
2 ⎠
7
nR
2
Using the following values
P1 = 2 [bar ]
P2 = 1 [bar ]
V1 = 10 [L]
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])⎢⎜⎜ 3.5 × 8.314 ⎢ ⎥ ⎟⎟ ln⎜⎜ ⎟⎟ − 8.314 ⎢ ln⎜⎜ ⎟⎟⎥
⎣⎝ ⎣ mol ⋅ K ⎦ ⎠ ⎝ 240.6 [K ] ⎠ ⎣ mol ⋅ K ⎥⎦ ⎝ 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 P1 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 ⎞k
V2 = ⎜⎜ 1 V1k ⎟⎟
⎝ P2 ⎠
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,
T1V1k −1
T2 =
V2k −1
Substitution of the appropriate variables provides
T2 = 197.4 [K ]
Now the entropy can be calculated,
⎡⎛ ⎡ J ⎤ ⎞ ⎛ 197.4 [K ] ⎞ ⎡ J ⎤ ⎛ 1 [bar ] ⎞⎤
∆S univ = ∆S sys = (1.0 [mol])⎢⎜⎜ 3.5 × 8.314 ⎢ ⎥ ⎟⎟ ln⎜⎜ ⎟⎟ − 8.314 ⎢ ln⎜⎜ ⎟⎟⎥
⎣⎝ ⎣ mol ⋅ K ⎦ ⎠ ⎝ 240.6 [K ] ⎠ ⎣ 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
Qsurr
∆S univ = ∆S sys + ∆S surr = m( sˆ2 − sˆ1 ) +
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
V2
W = − ∫ PE dV
V1
Since the piston expands at constant pressure, the above relationship becomes
W = − PE (V2 − V1 )
⎡ kJ ⎤
sˆ1 = 6.2119 ⎢ ⎥ (10 MPa, 400 ºC)
⎣ kg ⋅ K ⎦
⎡ m3 ⎤
vˆ1 = 0.02641 ⎢ ⎥ (10 MPa, 400 ºC)
⎣⎢ kg ⎦⎥
⎛
⎜
⎡ m3 ⎤ ⎞
V1 = m1vˆ1 = (3 kg)⎜ 0.02641 ⎢ ⎥ ⎟ = 0.07923 m
⎟
3
[ ]
⎝ ⎢⎣ kg ⎥⎦ ⎠
Now V2 and v2 are found as follows
W
V2 = V1 −
PE
= 0.07923 m3 −
− 748740 J
6
2.0 × 10 Pa
= 0.4536 m3 [ ]
V
ˆv2 = 2 =
0.4536 m 3
[ ]
= 0.1512 ⎢
⎡ m3 ⎤
⎥
m2 3 [kg ] ⎣⎢ kg ⎦⎥
14
Since v̂2 and P2 are known, state 2 is constrained. From the steam tables:
⎡ kJ ⎤ ⎛ ⎡ 3 ⎤⎞
sˆ2 = 7.1270 ⎢ ⎜ 20 bar, 0.1512 ⎢ m ⎥ ⎟
⎥ ⎜
⎣ kg ⋅ K ⎦ ⎝ ⎢⎣ kg ⎥⎦ ⎟⎠
Now ∆U will be evaluated, which is necessary for calculating Qsurr . From the steam tables:
⎡ kJ ⎤ ⎛ ⎡ 3 ⎤⎞
uˆ 2 = 2945.2 ⎢ ⎥ ⎜ 20 bar, 0.1512 ⎢ m ⎥ ⎟
⎣ kg ⎦ ⎜ ⎢⎣ kg ⎥⎦ ⎟⎠
⎝
⎡ kJ ⎤
uˆ1 = 2832.4 ⎢ ⎥ (100 bar, 400 º C)
⎣ kg ⎦
⎛ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞
∆U = m1 (uˆ 2 − uˆ1 ) = (3 [kg ])⎜⎜ 2945.2 ⎢ ⎥ − 2832.4 ⎢ ⎥ ⎟⎟ = 338.4 [kJ ]
⎝ ⎣ kg ⎦ ⎣ kg ⎦ ⎠
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
Qsurr
∆S univ = m( sˆ2 − sˆ1 ) +
Tsurr
⎛ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞ 1.09 × 103 [kJ ] ⎡ kJ ⎤
= (3 [kg ])⎜⎜ 7.1270 ⎢ ⎥ − 6 . 2119 ⎢ ⎥ ⎟− = 1.126 ⎢ ⎥
⎝ ⎣ kg K ⎦
⎟
⎣ kg K ⎦ ⎠ 673.15 [K ] ⎣K⎦
Therefore, this process is irreversible.
15
3.7
(a)
From Equation 3.63:
⎛T ⎞ ⎛P ⎞
∆s sys = c P ln⎜⎜ 2 ⎟⎟ − R ln⎜⎜ 2 ⎟⎟
⎝ T1 ⎠ ⎝ P1 ⎠
⎛ ⎡ J ⎤ ⎞ ⎡ 7 ⎛ 500 [K ] ⎞ ⎛ 0.5 [bar ] ⎞⎤ ⎡ J ⎤
∆s sys = ⎜⎜ 8.314 ⎢ ⎟⎟ ⎢ ln⎜⎜ ⎟⎟ − ln⎜⎜ ⎟⎟⎥ = 20.63 ⎢
⎝ ⎣ mol ⋅ K ⎦ ⎠ ⎣ 2 ⎝ 300 [K ] ⎠
⎥
⎝ 1 [bar ] ⎠⎦ ⎣ mol ⋅ K ⎥⎦
(b)
From Equation 3.65:
⎛T ⎞ ⎛v ⎞
∆s sys = cv ln⎜⎜ 2 ⎟⎟ + R ln⎜⎜ 2 ⎟⎟
⎝ T1 ⎠ ⎝ v1 ⎠
⎡ ⎛ ⎡ 3 ⎤ ⎞⎤
⎢ ⎜ 0.025 ⎢ m ⎥ ⎟⎥
⎜ ⎟
⎛ ⎡ J ⎤ ⎞ ⎢ 5 ⎛ 500 [K ] ⎞ ⎜ ⎣⎢ mol ⎦⎥ ⎟⎥ = 4.85 ⎡ J ⎤
∆s sys = ⎜⎜ 8.314 ⎢ ⎟
⎟ ⎢ ln ⎜
⎜ ⎟
⎟ + ln ⎥
⎝ ⎣ mol ⋅ K ⎥⎦ ⎠ ⎢ 2 ⎝ 300 [K ] ⎠ ⎜ ⎡ m 3 ⎤ ⎟⎥ ⎢⎣ mol ⋅ K ⎥⎦
⎢ ⎜ 0.05 ⎢ ⎥ ⎟⎥
⎜ ⎢ mol ⎥⎦ ⎟⎠⎦⎥
⎣⎢ ⎝ ⎣
(c)
First, we can find the molar volume of state 1 using the ideal gas law.
RT1 ⎡ m3 ⎤
v1 = = 0.025 ⎢ ⎥
P1 ⎣⎢ mol ⎦⎥
Now, we can use Equation 3.65
⎛T ⎞ ⎛v ⎞
∆s sys = cv ln⎜⎜ 2 ⎟⎟ + R ln⎜⎜ 2 ⎟⎟
⎝ T1 ⎠ ⎝ v1 ⎠
⎡ ⎛ ⎡ 3 ⎤ ⎞⎤
⎢ ⎜ 0.025 ⎢ m ⎥ ⎟⎥
⎛ ⎡ J ⎤ ⎞ ⎢ 5 ⎛ 500 [K ] ⎞ ⎜ ⎢⎣ mol ⎥⎦ ⎟⎥
⎟⎥ = 10.62 ⎡⎢
J ⎤
∆s sys = ⎜⎜ 8.314 ⎢ ⎥ ⎟
⎟ ⎢ ln ⎜
⎜ ⎟
⎟ + ln ⎜
⎝ ⎣ mol ⋅ K ⎦ ⎠ ⎢ 2 ⎝ 300 [K ] ⎠ ⎜ ⎡ m 3 ⎤ ⎟⎥ ⎣ 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 ºC 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 ºC and 0.6113 kPa is approximately equal to the
entropy at 0 ºC 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 ⎤
sˆ(0 º C , 1 atm ) ≅ sˆ(0.01 º C , 0.6113 kPa ) = 0 ⎢ ⎥
⎣ kg ⋅ K ⎦
⎡ kJ ⎤
sˆ(100 º C , 1 atm ) = 1.3068 ⎢ ⎥
⎣ kg ⋅ K ⎦
Therefore,
⎡ kJ ⎤ ⎡ kJ ⎤
∆sˆ = sˆ(100 º C , 1 atm ) − sˆ(0 º C , 1 atm ) = 1.3068 ⎢ ⎥ −0⎢ ⎥
⎣ kg ⋅ K ⎦ ⎣ kg ⋅ K ⎦
⎡ kJ ⎤
∆ŝ = 1.3068 ⎢ ⎥
⎣ kg ⋅ K ⎦
(ii). From the steam tables:
⎡ kJ ⎤
sˆl (100 º C , 1 atm ) = 1.3068 ⎢ ⎥
⎣ kg ⋅ K ⎦
⎡ kJ ⎤
sˆ v (100 º C , 1 atm ) = 7.3548 ⎢ ⎥
⎣ kg ⋅ K ⎦
Therefore,
⎡ kJ ⎤ ⎡ kJ ⎤
∆sˆ = sˆ v (100 º C , 1 atm ) − sˆ l (100 º C , 1 atm ) = 7.3548 ⎢ ⎥ − 1.3068 ⎢ ⎥
⎣ kg ⋅ K ⎦ ⎣ kg ⋅ K ⎦
⎡ kJ ⎤
∆ŝ = 6.048 ⎢ ⎥
⎣ 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 ]
vˆw ⎛ ⎡ m3 ⎤ ⎞
⎜ 0.001003 ⎢ ⎥ ⎟
⎜ ⎟
⎝ ⎣ kg ⎦ ⎠
nw =
mw
=
(0.399 [kg ]) = 22.15 [mol]
(MW )H 2O 0.0180148 ⎡ kg ⎤
⎢⎣ mol ⎥⎦
= 5.55 [mol]
mi
ni =
(MW )H 2O
Now, let’s assume that all of the ice melts in the process. (If the final answer is greater than 0
ºC, the assumption is correct.) The following expression mathematically represents the change
in internal energies (cP=cv).
[ ]
ni c P ,i (0 − (− )10 º C ) − ∆h fus + c P ,w (T f − 0 º C ) = −nw c P ,w (T f − 25 º 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 º 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
δqrev
∆s = ∫ T
initial
Assuming the heat capacities of ice and water are independent of temperature, the expressions
for the change in entropy of the subsystems are
⎛ 273.15 K ⎞ ∆h fus ⎛ 276.27 K ⎞

∆si = c P, i ln⎜ ⎟+ + c P, w ln⎜ ⎟
⎝ 263.15 K ⎠ 273.15 K ⎝ 273.15 K ⎠
⎛ 276.27 K ⎞
∆s w = c P, w ln⎜ ⎟
⎝ 298.15 K ⎠
Therefore
⎡ ⎛ 273.15 K ⎞ ∆h fus ⎛ 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 ⎤
sˆ1 = 6.2119 ⎢ ⎥ (400 ºC, 100 bar)
⎣ kg ⋅ K ⎦
⎡ kJ ⎤
sˆ2 = 8.5434 ⎢ ⎥ (400 ºC, 1 bar)
⎣ kg ⋅ K ⎦
Using the entropy criterion,
∆Suniv = 0 = m(sˆ2 − sˆ1 ) + ∆S surr

⎛ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞
∆S surr = −m(sˆ2 − sˆ1 ) = −(0.5 [kg ])⎜⎜ 8.5434 ⎢ ⎥ − 6.2119 ⎢ ⎥ ⎟⎟
⎝ ⎣ kg ⋅ K ⎦ ⎣ 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 ºC. 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 ⎤
uˆ1 = 2832.4 ⎢ ⎥ (400 ºC, 100 bar)
⎣ kg ⎦
⎡ kJ ⎤
uˆ 2 = 2967.8 ⎢ ⎥ (400 ºC, 1 bar)
⎣ kg ⎦
Therefore,
22
W = m(uˆ 2 − uˆ1 ) − Q
⎛ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞
W = (0 . 5 [kg ])⎜⎜ 2967 . 8 ⎢ ⎥ − 2832 . 4 ⎢ ⎥ ⎟⎟ − 784 . 76 [kJ ]
⎝ ⎣ kg ⎦ ⎣ kg ⎦ ⎠
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.
⎛P ⎞
W = nRT ln⎜⎜ 2 ⎟⎟
⎝ P1 ⎠
W=
(0.5 [kg ]) ⎛ ⎡ J ⎤⎞
⎜⎜ 8.3145 ⎢
⎛ 1 bar ⎞
⎟⎟(673.15 K )ln⎜
⎥ ⎟
⎛ ⎡ kg ⎤ ⎞ ⎝ ⎣ mol ⋅ K ⎦ ⎠ ⎝ 100 bar ⎠
⎜⎜ 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
P1 = Psurr +
(
2(5000 kg ) 9.81 m/s 2 ) = 24.6 ×105 Pa
2
0.05 m
Similarly, the final pressure is
P2 = Psurr +
(
3(5000 kg ) 9.81 m/s 2 ) = 34.4 × 105 Pa
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:
nRT2 nRT1
V2 = V1 = = 0.00169 m 3
P2 P1
Now, we can create one equation with one unknown:
⎛ nRT2 ⎞
n(5 / 2 R )(T2 − T1 ) = − P2 ⎜⎜ − V1 ⎟⎟
⎝ P2 ⎠
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:
⎛T ⎞ ⎛V ⎞ ⎛T ⎞ ⎛T P ⎞
∆suniv = ∆s sys = cv ln⎜⎜ 2 ⎟⎟ + R ln⎜⎜ 2 ⎟⎟ = (5 / 2 R )ln⎜⎜ 2 ⎟⎟ + R ln⎜⎜ 2 1 ⎟⎟
⎝ T1 ⎠ ⎝ V1 ⎠ ⎝ T1 ⎠ ⎝ T1P2 ⎠
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 34.4 bar

500 K 557 K
rev.
State 1 adiabatic 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:
T1P1(1− k ) / k = TI PI(1− k ) / k = T2 PI(1− k ) / k
Therefore,
k
⎛ T ⎞ (1− k )
PI = ⎜⎜ 1 ⎟⎟ P1 = 35.9 [bar] (I)
⎝ T2 ⎠
If we draw the process on a PT diagram, we get:

40
P
I
2
Adiabatic compression Isothermal

expansion
20
490 560
T
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,
RT
δq rev = −δwrev = − dP
P
Therefore,
δq ⎛P ⎞
final P2
R ⎡ J ⎤
∆s sys = ∫
initial
T
= ∫−
PI
P
dP = − R ln⎜⎜ 2 ⎟⎟ = 0.354 ⎢
⎝ PI ⎠ ⎣ mol ⋅ K ⎥⎦
If we substitute relation (I) in the expression above, we get the same expression in the book:
⎛P ⎞ k ⎛T ⎞ ⎛T ⎞ ⎛P ⎞
∆s sys = − R ln⎜⎜ 2 ⎟⎟ + R ln⎜⎜ 2 ⎟⎟ = c P ln⎜⎜ 2 ⎟⎟ − R ln⎜⎜ 2 ⎟⎟
⎝ P1 ⎠ (1 − k ) ⎝ T1 ⎠ ⎝ T1 ⎠ ⎝ P1 ⎠
(b)
For this construction, we use the path diagrammed on the following PT diagram:
40
P
Isothermal
compression
Isobaric heating
20
490 560
T
We write
27
∆s sys = ∆sisobar + ∆sisothermal
First, find an expression for the isobaric heating
δq rev = dh = c P dT
Therefore,
T2
c ⎛T ⎞
∆sisobar = ∫ TP dT = c P ln⎜⎜⎝ T12 ⎟⎟⎠
T1
Now, we need an expression for the isothermal, reversible expansion
δq rev = −δwrev = Pdv
Therefore,
v 2 = RT2 / P2 v 2 = RT2 / P2
P R ⎛P ⎞ ⎛P ⎞
∆sisothermal = ∫ T
dv = ∫ v
dv = R ln⎜⎜ 1 ⎟⎟ = − R ln⎜⎜ 2 ⎟⎟
⎝ P2 ⎠ ⎝ P1 ⎠
v I = RT2 / P1 v1 = RT2 / P1
Combine the two steps:
⎛T ⎞ ⎛P ⎞ ⎡ J ⎤
∆s sys = c P ln⎜⎜ 2 ⎟⎟ − R ln⎜⎜ 2 ⎟⎟ = 0.354 ⎢
⎝ T1 ⎠ ⎝ P1 ⎠ ⎣ mol ⋅ K ⎥⎦
(c)
For this construction, we use the path diagrammed on the following PT diagram:
28
40
P
Isothermal
compression
Isochoric heating I
20
490 560
T
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)
⎛P ⎞
∆sisothermal = − R ln⎜⎜ 2 ⎟⎟
⎝ PI ⎠
However, we can relate the intermediate pressure to the initial pressure through the ideal gas law:
PI P1
=
T2 T1
or
PI = 27.4 [bar]
⎛ ⎞
⎜ ⎟
⎛ P2 ⎞ ⎜ P2 ⎟ ⎛T ⎞ ⎛P ⎞
∴ ∆sisothermal = − R ln⎜⎜ ⎟⎟ = − R ln = R ln⎜⎜ 2 ⎟⎟ − R ln⎜⎜ 2 ⎟⎟
⎝ PI ⎠ ⎜ T2 ⎟ ⎝ T1 ⎠ ⎝ P1 ⎠
⎜ P1 ⎟
⎝ T1 ⎠
For the isochoric process:
δq rev = cv dT
Therefore,
29
T2
cv ⎛T ⎞
∆sisochoric = ∫ T dT = cv ln⎜⎜⎝ T12 ⎟⎟⎠
T1
Combining these results:
⎛T ⎞ ⎛P ⎞ ⎛T ⎞ ⎛P ⎞ ⎡ J ⎤
∆s sys = (cv + R ) ln⎜⎜ 2 ⎟⎟ − R ln⎜⎜ 2 ⎟⎟ = c P ln⎜⎜ 2 ⎟⎟ − R ln⎜⎜ 2 ⎟⎟ = 0.354 ⎢
⎝ T1 ⎠ ⎝ P1 ⎠ ⎝ T1 ⎠ ⎝ P1 ⎠ ⎣ mol ⋅ K ⎥⎦
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 − Rln 2
T T 1
P1
Insert the expression for cP from Appendix A
3.639 + 0.506 ×10 −3 T − 0.227 ×10 −6 T 2 ⎛P ⎞

T2
∆s = 0 = R ∫ dT − R ln⎜⎜ 2 ⎟⎟
T1
T ⎝ P1 ⎠
which upon substituting
T1 = 250 [K ]
P1 = 1 [bar ]
P2 = 12.06 [bar ]
yields
T2 = 482 [K ]
(c)
An energy balance gives
T2 T2
w = ∆u = ∫ cv dT =
T1
∫ (c
T1
P − 1)dT
31
w = R ∫ (2.639 + 0.506 × 10 −3 T − 0.227 × 10 −6 T 2 )dT = 5390 ⎢
T2
⎡ J ⎤
T1 ⎣ mol ⎥⎦
(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
∆U = m(uˆ 2 − uˆ1 ) = 0
∴ 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 ⎤
uˆ1 = 2619.2 ⎢ ⎥ (400 ºC, 200 bar)
⎣ kg ⎦
⎡ kJ ⎤
∴ uˆ 2 = 2619.2 ⎢ ⎥
⎣ kg ⎦
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 ⎤
sˆ1 = 5.5539 ⎢ ⎥ (400 ºC, 200 bar)
⎣ kg ⋅ K ⎦
⎡ kJ ⎤ ⎛ ⎡ kJ ⎤ ⎞
sˆ2 = 5.7754 ⎢ ⎥ ⎜100 bar, uˆ 2 = 2619.2 ⎢ ⎥ ⎟
⎜ ⎟
⎣ kg ⋅ K ⎦ ⎝ ⎣ kg ⎦ ⎠
Therefore,
⎡ kJ ⎤
∆sûniv = ∆sˆsys = sˆ2 − sˆ1 = 0.2215 ⎢ ⎥
⎣ 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 ⎤⎞
⎜⎜ 8.314 ⎢ ⎟⎟(300 [K ])
⎝ ⎣ mol ⋅ K ⎥⎦ ⎠
Now, the change in entropy can be solved using a slight modification of Equation 3.65:
⎡ ⎛T ⎞ ⎛ v ⎞⎤ ⎡3 ⎛T ⎞ ⎛ nv ⎞⎤
∆S sys = n ⎢cv ln⎜⎜ 2 ⎟⎟ + R ln⎜⎜ 2 ⎟⎟⎥ = n ⎢ R ln⎜⎜ 2 ⎟⎟ + R ln⎜⎜ 2 ⎟⎟⎥
⎣ ⎝ T1 ⎠ ⎝ v1 ⎠⎦ ⎣2 ⎝ T1 ⎠ ⎝ nv1 ⎠⎦
⎛ ⎡ J ⎤ ⎞⎡ 3 ⎤
∆S sys = (200.5 mol)⎜⎜ 8.314 ⎢ ⎥ ⎟⎟ ⎢ ln(1) + ln(2)⎥
⎝ ⎣ mol ⋅ K ⎦ ⎠ ⎣ 2 ⎦
⎡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 O2 N2 N2
N2
Mixing
Process
N2 N2 O2
N2
N2 O2 N2
N2 N2
N2 N2 O2 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
cP ⎛ P2 ⎞ ⎛ ⎡ J ⎤ ⎞ ⎛ 0.79 bar ⎞
∆s sys, N 2 = ∫ T dT − R ln ⎜⎜ ⎟⎟ = −⎜⎜ 8.314 ⎢
⎝ P1 ⎠ N ⎝ ⎣
⎟ ln⎜ ⎟
mol ⋅ K ⎥⎦ ⎟⎠ ⎝ 1 bar ⎠
298 K 2
⎡ J ⎤
∆s sys, N 2 = 1.96 ⎢
⎣ mol ⋅ K ⎥⎦
298 K
cP ⎛P ⎞ ⎛ ⎡ J ⎤ ⎞ ⎛ 0.21 bar ⎞
∆s sys, O2 = ∫ T
dT − R ln⎜⎜ 2 ⎟⎟ = −⎜⎜ 8.314 ⎢
⎝ P1 ⎠O ⎝ ⎣
⎟ ln⎜ ⎟
mol ⋅ K ⎥⎦ ⎟⎠ ⎝ 1 bar ⎠
298 K 2
⎡ J ⎤
∆s sys ,O2 = 12.98 ⎢
⎣ mol ⋅ K ⎥⎦
Therefore,
⎛ ⎡ J ⎤⎞ ⎛ ⎡ J ⎤⎞
∆S univ = (0.79 mol)⎜⎜1.96 ⎢ ⎥ ⎟⎟ + (0.21 mol)⎜⎜12.98 ⎢ ⎟⎟
⎝ ⎣ mol ⋅ K ⎦ ⎠ ⎝ ⎣ 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 O2 N2 N2
N2 Mixing
N2 N2 Process N2
N2 N2
N2 N2
N2 N2 O2
N2 O2 O2 N2
N2 N2
N2 N2 N2 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 2
)
+ 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
+
nO2
=
(nO 2
+ nN 2 )
P1, N 2 P1, O2 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
cP ⎛P ⎞ ⎛ ⎡ J ⎤ ⎞ ⎛ 1.30 bar ⎞
∆s sys, N 2 = ∫
T
dT − R ln⎜⎜ 2 ⎟⎟ = −⎜⎜ 8.314 ⎢
⎝ P1 ⎠ N ⎝ ⎣
⎟ ln⎜ ⎟
mol ⋅ K ⎥⎦ ⎟⎠ ⎝ 2 bar ⎠
298 K 2
⎡ J ⎤
∆s sys, N 2 = 3.58 ⎢
⎣ mol ⋅ K ⎥⎦
298 K
cP ⎛P ⎞ ⎛ ⎡ J ⎤ ⎞ ⎛ 0.347 bar ⎞
∆ssys ,O2 = ∫
298 K
T
dT − R ln⎜⎜ 2 ⎟⎟ = −⎜⎜ 8.314 ⎢
⎝ P1 ⎠O2 ⎝
⎟⎟ ln⎜ ⎟
⎣ mol ⋅ K ⎥⎦ ⎠ ⎝ 1 bar ⎠
⎡ J ⎤
∆s sys ,O2 = 8.8 ⎢
⎣ mol ⋅ K ⎥⎦
Therefore,
⎛ ⎡ J ⎤⎞ ⎛ ⎡ J ⎤⎞
∆S univ = (0.79 mol)⎜⎜ 3.58 ⎢ ⎥ ⎟⎟ + (0.21mol)⎜⎜ 8.8 ⎢ ⎟⎟
⎝ ⎣ mol ⋅ K ⎦ ⎠ ⎝ ⎣ 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& 2 hˆ2 = m& 1hˆ1
A mass balance allows the energy balance to be simplified to
hˆ2 = hˆ1
⎡ kJ ⎤
hˆ1 = 3398.3 ⎢ ⎥ (500 ºC, 8 MPa)
⎣ kg ⎦
⎡ kJ ⎤
∴ hˆ2 = 3398.3 ⎢ ⎥
⎣ kg ⎦
Now calculate entropy:
∆sûniv = ∆sˆsys + ∆sˆsurr
Since the process is adiabatic,
⎡ kJ ⎤
∆sˆsurr = 0 ⎢ ⎥
⎣ kg ⋅ K ⎦
The steam tables can be used to calculate the change in entropy of the system.
⎡ kJ ⎤ ⎛ ⎡ kJ ⎤ ⎞
sˆ2 = 8.7098 ⎢ ⎥ ⎜100 kPa, hˆ2 = 3398.3 ⎢ ⎥ ⎟
⎜ ⎟
⎣ kg ⋅ K ⎦ ⎝ ⎣ kg ⎦ ⎠
⎡ kJ ⎤
sˆ1 = 6.7239 ⎢ ⎥ (8 MPa, 500 ºC)
⎣ kg ⋅ K ⎦
Thus,
⎡ kJ ⎤
∆sûniv = ∆sˆsys = sˆ2 − sˆ1 = 1.9859 ⎢ ⎥
⎣ kg ⋅ K ⎦
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
m& 1 = m& 2 + m& 3
⎡ 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& 2 hˆ2 + m& 3hˆ3 − m& 1hˆ1 = 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:
( ) ( )
m& 2 hˆ2 − hˆ1 + m& 3 hˆ3 − hˆ1 = 0
If we assume that the heat capacity of the ideal gas is constant, the equation can be written as
follows:
m& 2 cˆP (T2 − T1 ) + m& 3cˆP (T3 − T1 ) = 0
Therefore,
⎡ kg ⎤ ⎡ kg ⎤
0.5 ⎢ ⎥ cˆP (−60 K) + 1.5 ⎢ ⎥ cˆP (20 K) = 0
⎣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 ⎞
⎜ ⎟ = m& 2 sˆ2 + m& 3 sˆ3 − m& 1sˆ1 = m& 2 (sˆ2 − sˆ1 ) + m& 3 (sˆ3 − sˆ1 )
⎝ dt ⎠univ
39
where a mass balance was used. For constant heat capacity, we can calculate the entropy
differences using Equation 3.63:
⎛T ⎞ ⎛P ⎞ ⎡5 ⎛ T ⎞ ⎛ P ⎞⎤
s2 − s1 = cP ln⎜⎜ 2 ⎟⎟ − R ln⎜⎜ 2 ⎟⎟ = R ⎢ ln⎜⎜ 2 ⎟⎟ − ln⎜⎜ 2 ⎟⎟⎥
⎝ T1 ⎠ ⎝ P1 ⎠ ⎣ 2 ⎝ T1 ⎠ ⎝ P1 ⎠⎦
⎛T ⎞ ⎛P ⎞ ⎡5 ⎛ T ⎞ ⎛ P ⎞⎤
s3 − s1 = cP ln⎜⎜ 3 ⎟⎟ − R ln⎜⎜ 3 ⎟⎟ = R ⎢ ln⎜⎜ 3 ⎟⎟ − ln⎜⎜ 3 ⎟⎟⎥
⎝ T1 ⎠ ⎝ P1 ⎠ ⎣ 2 ⎝ T1 ⎠ ⎝ P1 ⎠⎦
Applying these relations, we get:
⎛ dS ⎞
⎜ ⎟ =
1
(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 P2 = 100 kPa
V1= 20 m/s V2=?

Nozzle
(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 ⎤
sˆ2 = sˆ1 (640 º C, 4 MPa ) = 7.4692 ⎢ ⎥
⎣ kg ⋅ K ⎦
Now two thermodynamic properties are known for state 2. From the steam tables:
⎛ ⎡ kJ ⎤ ⎞
T2 = 121.4 º C ⎜ P2 = 0.1 MPa, sˆ2 = 7.4692 ⎢ ⎥ ⎟⎟
⎜ ⋅
⎝ ⎣ kg K ⎦⎠
(d)
An energy balance is required to calculate the exit velocity. The energy balance for the nozzle is
( ) ( )
0 = m& 2 hˆ + eˆK 2 − m& 1 hˆ + eˆ K 1
Realizing that m& 1 = m& 2 allows the energy balance to be written as
( )
eˆK ,2 = hˆ + eˆ K 1 − hˆ2
which is equivalent to
r
[(
r
)
V2 = 2 hˆ + 0.5V 2 1 − hˆ2 ]
Substituting the following values
41
r ⎡m⎤
V1 = 20 ⎢ ⎥
⎣s⎦
⎡ J ⎤
hˆ2 = 2719100 ⎢ ⎥ (0.1 MPa, 121.4 ºC)
⎣ kg ⎦
⎡ J ⎤
hˆ1 = 3767000 ⎢ ⎥ (4 MPa, 640 ºC)
⎣ kg ⎦
yields
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 Turbine ws

T1= 350 oC
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 − Rln 2
T T 1
P1
Insert the expression for cP from Appendix A
1.213 + 28.785 × 10 −3 T − 8.824 × 10 −6 T 2 ⎛P ⎞

T2
∆s = 0 = R ∫ dT − R ln⎜⎜ 2 ⎟⎟
T1
T ⎝ P1 ⎠
We can also relate P1 to T1 and v1 (which are known) through the ideal gas law:
RT1
P1 =
v1
This leaves us with 1 equation and 1 unknown (T2). Integrating:
⎛T ⎞ ⎛Pv ⎞
( )
∆s = 0 = 1.213 ln⎜⎜ 2 ⎟⎟ + 28.785 × 10 −3 (T2 − T1 ) − 4.412 ×10 −6 T22 − T12 − ln⎜⎜ 2 1 ⎟⎟
⎝ T1 ⎠ ⎝ RT1 ⎠
Using
T1 = 623 K,
v1 = 600 cm3/mol,
P2 = 1 atm
43
R=82.06 cm3 atm/mol K,
we get:
T2 = 454 K
W& S
To solve for we need a first law balance, with negligible ke and pe, the 1st law for a steady
n&
state process becomes:
0 = n& (h1 − h2 ) + Q& + W& S
If heat transfer is negligible (isentropic),
W& S
( )
T2 T2
= h2 − h1 = ∫ c p dT = R ∫ 1.213 + 28.785 × 10 −3 T − 8.824 × 10 −6 T dT

2
n& T1 T1
integrating:
W& S
&n
[ ( ) (
= R 1.213(T2 − T1 ) + 14.393 ×10 − 3 T22 − T12 − 2.941×10 − 6 T23 − T13 )]
Substituting
⎡ J ⎤
R = 8.314 ⎢
⎣ mol ⋅ K ⎥⎦
T2 = 454 K
T1 = 623 K
results in
W& S ⎡ J ⎤
= −19860 ⎢
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
T2 (c
P )O2 ⎛P ⎞
∆sO2 = ∫ T
dT − R ln⎜⎜ 2 ⎟⎟
⎝ P1 ⎠
T1 O2
T2 (c
P )N 2 ⎛P ⎞
∆s N 2 = ∫ T
dT − R ln⎜⎜ 2 ⎟⎟
⎝ P1 ⎠
T1 N2
Since the temperature of the streams do not change, the expressions reduce to
⎛P ⎞
∆sO2 = − R ln⎜⎜ 2 ⎟⎟
⎝ P1 ⎠ O2
⎛P ⎞
∆s N 2 = − R ln⎜⎜ 2 ⎟⎟
⎝ P1 ⎠ N 2
Therefore,
⎡ ⎛ P2 ⎞ ⎛P ⎞ ⎤
∆ s surr = R ⎢ ln ⎜⎜ ⎟⎟ + ln ⎜⎜ 2 ⎟⎟ ⎥
⎢ ⎝ P1 ⎠O2 ⎝ P1 ⎠ N 2 ⎥
⎣ ⎦
Since we are assuming the temperature of the surroundings remain constant at 20 ºC,
q
∆s surr = surr
Tsurr
where
− qsurr = q
45
Therefore,
⎡ ⎛P ⎞ ⎛ P2 ⎞ ⎤
q surr = Tsurr ∆s surr = RTsurr ln⎜ ⎟ + ln⎜⎜ ⎟⎟ ⎥
⎢ ⎜ 2 ⎟
⎢ ⎝ P1 ⎠ O ⎝ P1 ⎠ N 2 ⎥⎦
⎣ 2
⎛ ⎡ J ⎤⎞ ⎡ ⎛ 1 bar ⎞ ⎛ 1 bar ⎞ ⎤
q surr = ⎜⎜ 8.314 ⎢ ⎟
⎟ (293 . 15 K )⎢ ln ⎜ ⎟ + ln ⎜ ⎟ ⎥
⎝ ⎣ mol ⋅ K ⎥⎦ ⎠ ⎢⎣ ⎝ 0.21 bar ⎠ O2 ⎝ 0.79 bar ⎠ N 2 ⎥⎦
⎡ J ⎤
q surr = 4378.2 ⎢
⎣ mol ⎥⎦
and
⎡ J ⎤
q = −4378.2 ⎢
⎣ mol ⎥⎦
Energy Balance:
∑ n&
in
h −∑ n&out hout + Q& + W& S = 0
in in
out
Because the temperature of the oxygen and nitrogen doesn’t 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, let’s 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
( )
T
⎡3 ⎤
2.41⎢ R(T2 − 773.15 K )⎥ + R ∫ 5/2 + 1.5 × 10-3 T dT = 0
2
⎣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
T2 ⎛⎜ PA,1 2 PB ,1 ⎞⎟ 585 [K ] ⎛ 10 [bar ] 1 [bar ] ⎞

P2 = + = ⎜⎜ +2 ⎟
⎜
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:
n1, A n1,B
∆ssys = ∆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 ,
2.41 ⎡ ⎛T ⎞ ⎛ P ⎞⎤ ⎡ J ⎤
∆sgas A = ⎢2.5 R ln⎜⎜ 2 ⎟⎟ − R ln⎜⎜ 2 ⎟⎟⎥ = 1.96 ⎢
3.41 ⎢⎣ ⎝ TA,1 ⎠ ⎝ PA,1 ⎠⎥⎦ ⎣ mol ⋅ K ⎥⎦
1 ⎡ 2 3.5 + 1.5 × 10 −3 T ⎛ P ⎞⎤
T
⎡ J ⎤
∆sgas B = ⎢R ∫ dT − R ln⎜⎜ 2 ⎟⎟⎥ = 1.51 ⎢
3.41 ⎢ TB ,1
⎣
T ⎝ PB ,1 ⎠⎥⎦ ⎣ mol ⋅ K ⎥⎦
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
Let’s 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 ºC), the water’s entropy is
constrained. From the steam tables,
⎡ kJ ⎤
vˆ1l, i = 0.001156 ⎢ ⎥
⎣ kg ⎦
⎡ kJ ⎤
vˆ1v, i = 0.12736 ⎢ ⎥
⎣ kg ⎦
⎡ kJ ⎤
sˆ1l, i = 2.3308 ⎢ ⎥ (Sat. water at 200 ºC)
⎣ kg ⎦
⎡ kJ ⎤
sˆ1v, 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.
( ) ( )
V1 = 0.05m1 vˆ1l, i + 0.95m1 vˆ1v,i
[ ]
Using the values from the steam table and V1 = 0.5 m 3 provides
m1 = 4.13 [kg ]
Using the water quality specification,
49
m1v = 0.95m1 = 3.92 [kg ]
m1l = 0.05m1 = 0.207 [kg ]
For the piston-cylinder assembly, both P and T are known. From the steam tables
⎡ m3 ⎤
vˆ2, i = 0.35202 ⎢ ⎥
⎢⎣ kg ⎥⎦
(600 kPa, 200 ºC)
⎡ kJ ⎤
sˆ2, i = 6.9665 ⎢ ⎥
⎣ kg ⋅ K ⎦
Now enough information is available to calculate the mass of water in the piston assembly.
m2 = 2 = 0.284 [kg ]
V
vˆ2
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 ºC, the final temperature and pressure of
the entire system will match the surrounding’s. In other words,
⎡ kJ ⎤
sˆ f = sˆ2, i = 6.9665 ⎢ ⎥ (600 kPa, 200 ºC)
⎣ kg ⎦
Thus, the change in entropy is given by
∆S sys = (m2 + m1v, i + m1l, i ) sˆ f − m2 sˆ2, i − m1v, i sˆ1v, i − m1l, i sˆ1l, i
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,
Qsurr −Q
∆S surr = =
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.
∆U = (m2 + m1v, i + m1l, i )uˆ f − m2 uˆ 2, i − m1v, i uˆ1v, i − m1l, i uˆ1l, i
⎡ kJ ⎤
uˆ1l, i = 850.64 ⎢ ⎥
⎣ kg ⎦
(sat. H2O at 200 ºC)
⎡ kJ ⎤
uˆ1v, i = 2595.3 ⎢ ⎥
⎣ kg ⎦
⎡ kJ ⎤
uˆ f = uˆ 2, i = 2638.9 ⎢ ⎥ (600 kPa, 200 ºC)
⎣ kg ⎦
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,
Vf
W = − PE ∫ dV = − PE (V f − Vi )
Vi
where
PE = 600000 [Pa ]
V f = (m2 + m1v, i + m1l,i )vˆ2, i = 1.55 m 3 [ ]
[ ] [ ]
Vi = 0.1 m 3 + 0.5 m 3 = 0.6 m 3 [ ]
Note: vˆ2, i was used to calculate V f because the temperature and pressure are the same
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,
− 1111 [kJ ] ⎡ kJ ⎤
∆S surr = = −2.35 ⎢ ⎥
473.15 [K ] ⎣K⎦
and
⎡ kJ ⎤ ⎡ kJ ⎤ ⎡ kJ ⎤
∆Suniv = ∆S sys + ∆S surr = 3.05 ⎢ ⎥ − 2.35 ⎢ ⎥ = 0.70 ⎢ ⎥
⎣K⎦ ⎣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 ⎥⎦ ⎠
[ ]
( [ ])
V1, a = = 0.05 m 3
⎡ (1000 [kg ]) 9.8 m ⋅ s - 2 ⎤
⎢
⎣⎢ [ ]
0.098 m 2
⎥
⎦⎥
(4 [mol])⎛⎜⎜ 8.314 ⎡⎢ J ⎤⎞
⎟⎟T2
⎝ ⎣ mol ⋅ K ⎥⎦ ⎠
= 3.3256 × 10 − 4 T2 m 3[ ]
( [ ])
V2 =
⎡ (1000 [kg ]) 9.8 m ⋅ s ⎤
- 2
⎢
⎣⎢ 0.098 m 2 [ ] ⎥
⎦⎥
Substitute the volumes into the energy balance and solve for T2 :
(2 mol)⎛⎜ 3 R ⎞⎟(T2 − 300 K ) + (2 mol)⎛⎜ 3 R ⎞⎟(T2 − 300 K ) = −(1× 105 Pa )[3.3256 × 10 − 4 T2 − 0.15 m 3 ]
⎝2 ⎠ ⎝2 ⎠
T2 = 360.4 K
To calculate the change in entropy, we can use the following relationship
⎡ ⎛T ⎞ ⎛ P ⎞⎤ ⎡ ⎛T ⎞ ⎛ P ⎞⎤
∆S sys = na ⎢c P ln⎜⎜ 2 ⎟⎟ − R ln⎜⎜ 2 ⎟⎟⎥ + nb ⎢c P ln⎜⎜ 2 ⎟⎟ − R ln⎜⎜ 2 ⎟⎟⎥
⎣ ⎝ T1 ⎠ ⎝ P1 ⎠⎦ a ⎣ ⎝ T1 ⎠ ⎝ P1 ⎠⎦ b
The only unknown in the above equation is P1,b, so we can calculate it with the ideal gas law:
53
(2 mol)⎛⎜⎜ 8.314 ⎡⎢ J ⎤⎞
⎟⎟(300 K )
⎝ ⎣ mol ⋅ K ⎥⎦ ⎠
P1, b = = 0.5 × 10 5 Pa
3
0 .1 m
Substitute values into the expression for entropy and solve:
⎡ 5 ⎛ 360.4 K ⎞ ⎛ 1 bar ⎞⎤ ⎡ 5 ⎛ 360.4 K ⎞ ⎛ 1 bar ⎞⎤

∆S sys = (2 mol)R ⎢ ln⎜ ⎟ − ln⎜ ⎟⎥ + (2 mol)R ⎢ ln⎜⎜ ⎟⎟ − ln⎜ ⎟⎥
⎣ 2 ⎝ 300 K ⎠ ⎝ 1 bar ⎠⎦ a ⎣ 2 ⎝ 300 K ⎠ ⎝ 0.5 bar ⎠⎦ b
⎡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
5
Using the ideal gas law and cv = 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
Vf
W = − ∫ PE dV
Vi
The pressure is not constant; its value is given by
kx mg k (VB − VB ,i ) mg
PE = Patm + + = Patm + +
A A A2 A
PE = 1.06 × 10 + 8.284 × 10 VB [Pa ]
5 5
Integrating
W = −1.06 ×105VB, f − 4.142 ×105VB2, f
Substituting this expression into the energy balance gives:
5 5 5
PB, f VB, f + PA, f V A, f − PA,iV A, i = −1.06 × 105VB, f − 4.142 × 105VB2, 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
2
( ) 5
PB, f VB, f + V A, i − PA, iV A, i = −1.06 ×105VB, f − 4.142 × 105VB2, f
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
2
( )( 5
)
1.06 × 105 + 8.284 ×105VB, f VB, f + V A, i − PA, iV A, i = −1.06 ×105VB, f − 4.142 ×105VB2, f
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,
⎛T ⎞ ⎛P ⎞
0 = c P ln⎜⎜ 2 ⎟⎟ − R ln⎜⎜ 2 ⎟⎟
⎝ T1 ⎠ ⎝ P1 ⎠
⎛ ⎡ J ⎤ ⎞ ⎡ 7 ⎛ T2 ⎞ ⎛ 3.28 × 10 5 Pa ⎞⎤
0 = ⎜⎜ 8.314 ⎢ ⎟⎟ ⎢ ln⎜ ⎟ − ln⎜ ⎟⎥
⎝ ⎣ mol ⋅ K ⎥⎦ ⎠ ⎢⎣ 2 ⎝ 313.15 K ⎠ ⎜ 7.0 × 10 5 Pa ⎟⎥
⎝ ⎠⎦
Solve for T2:
T2 = 252 K
56
3.26
A schematic of the process is drawn:
Q surr=69.86 kW
Steam
in W
P1 = 60 bar Turbine
T1 = 500 oC Steam
out P2 = 10 bar
Tsurr=300 K
(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
Q& surr
m& (sˆ2 − sˆ1 ) + =0
Tsurr
Calculate the change in entropy of the surroundings:
⎡ kJ ⎤
We can look up property values of state 1 from the steam tables sˆ1 = 6.8802 ⎢ ⎥ and
⎣ kgK ⎦
⎡ kJ ⎤
hˆ1 = 3,422.13 ⎢ ⎥ . Converting the units of mass flow rate gives:
⎣ kg ⎦
⎛ ⎡ kg ⎤ ⎞⎛ 1 [hr ] ⎞ ⎡ kg ⎤
m& = ⎜⎜ 4,500 ⎢ ⎥ ⎟⎟⎜⎜ ⎟⎟ = 1.25 ⎢ ⎥
⎝ ⎣ hr ⎦ ⎠⎝ 3,600 [s] ⎠ ⎣ s ⎦
so
Q& surr ⎡ kJ ⎤
sˆ2 = sˆ1 − = 6.6939 ⎢ ⎥
m& Tsurr ⎣ kgK ⎦
We now know two properties of steam ( ŝ2 and P2) From the steam tables:
T2 = 200 oC
Using the steam tables for superheated steam at 1 MPa, we find that when water has this value of
entropy
57
⎡ kJ ⎤
hˆ2 = 2827.9 ⎢ ⎥
⎣ kg ⎦
Energy balance:
( )
m& hˆ2 − hˆ1 = Q& + W& s
Calculate Ws:
( ) ⎛ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞
W& s = m& hˆ2 − hˆ1 − Q& = (1.25 kg/s )⎜⎜ 2827.9 ⎢ ⎥ − 3422.1 ⎢ ⎥ ⎟⎟ − (− )69.86 [kW ]
⎝ ⎣ kg ⎦ ⎣ kg ⎦ ⎠
W& s = −673 [kW ]
(c)
The isentropic efficiency is defined as follows:
η=
(W& S )actual
(W& S )reversible
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:
( )
m& hˆ2 − hˆ1 = Q& + W& s
Q& + W& s ˆ − 69.86 kW + -447.5 kW ⎡ kJ ⎤ ⎡ kJ ⎤
hˆ2 = + h1 = + 3422.1 ⎢ ⎥ = 3008.2 ⎢ ⎥
m& 1.25 kg/s ⎣ kg ⎦ ⎣ kg ⎦
At 1 MPa, water has this value of enthalpy when
(T2 )actual = 280.2 º C
58
3.27
Since the compressor is adiabatic, the energy balance after neglecting potential and kinetic
energy becomes
n& (h2 − h1 ) = W& S
Using the ideal gas law and Appendix A.2, the above equation becomes
( )
T
P1V&1 2
A + BT + CT 2 + DT − 2 + ET 3 dT
T1 ∫
&
WS =
T1
Substituting the following values
P1 = 1 [bar ] = 1× 105 [Pa ]

⎡ m3 ⎤
V&1 = 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
W& S = 218.8 [kW ]
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.
(W& )
ηcompressor = & S reversible
(WS ) compressor
(W& S )reversible = (W& S )compressor ηcompressor = (0.8)(218.8 [kW ])
(W& S )reversible = 175.4 [kW ]
Since the process is adiabatic, we can use the following equation again to calculate what the final
temperature would be in a reversible process.
( )
T
P1V&1 2
&
WS = ∫ A + BT + CT 2 + DT − 2 + ET 3 dT
T1
T1
59
∫ (A + BT + CT )
T2
P V&
∴175400 [W ] = 1 1 2
+ DT − 2 + ET 3 dT
T1
T1
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
cp ⎛P ⎞
∆s = 0 = ∫ T
dT − R ln⎜⎜ 2 ⎟⎟
⎝ P1 ⎠
T1
⎡ A + BT + CT 2 + DT − 2 + ET 3 ⎤
T2
⎛P ⎞
∆s = 0 = R ∫ ⎢ ⎥ dT − R ln⎜⎜ 2 ⎟⎟
T1 ⎢⎣
T ⎥⎦ ⎝ P1 ⎠
⎡ T2 = 438 K ⎡
∆s = 0 = R ⎢ ∫ ⎢⎢
( )
3.355 + 0.575 × 10 − 3 T − 1600T − 2 ⎤
⎥ dT − ln
⎛ P2 ⎞⎥
⎜ ⎟
⎜ [1 bar ] ⎟⎥
⎤
⎢ T ⎥⎦ ⎝ ⎠
⎣ 1
T = 293 .15 K ⎣ ⎦
Solve for P2:
P2 = 4.16 [bar ]
60
3.28
Isentropic efficiency for a turbine is defined as
(ws )actual
η=
(ws )rev
If the rate of heat transfer is assumed negligible, the energy balance for this process is
( )
0 = m& hˆ1 − hˆ2 + W& s
For a reversible, adiabatic process,
∆s sys = 0
sˆ2,rev = sˆ1 (500 º C, 10 MPa )
⎡ kJ ⎤
sˆ2,rev = sˆ1 = 6.5965 ⎢ ⎥
⎣ kg ⋅ K ⎦
Since sˆ2l , sat ≤ sˆ2 ≤ sˆ2v, sat , a mixture of liquid and vapor exists. The quality of the water can be
calculated as follows
sˆ2,rev = (1 − x )sˆ2l ,sat + xsˆ2v ,sat

⎡ kJ ⎤ ⎛ ⎡ kJ ⎤ ⎞ ⎛ ⎡ kJ ⎤ ⎞
6.5965 ⎢ ⎥ = (1 − x )⎜⎜1.3025 ⎢ ⎥ ⎟ + x⎜ 7.3593 ⎢
⎟ ⎜ ⎥ ⎟⎟
⎣ kg ⋅ K ⎦ ⎝ ⎣ kg ⋅ K ⎦ ⎠ ⎝ ⎣ kg ⋅ K ⎦⎠
x = 0.874
Therefore,
hˆ2,rev = (1 − x )hˆ2l ,sat + xhˆ2v ,sat

⎛ ⎡ kJ ⎤ ⎞ ⎛ ⎡ kJ ⎤ ⎞
hˆ2,rev = (1 − 0.874 )⎜⎜ 417.44 ⎢ ⎥ ⎟⎟ + 0.874⎜⎜ 2675.5 ⎢ ⎥ ⎟⎟
⎝ ⎣ kg ⎦ ⎠ ⎝ ⎣ kg ⎦ ⎠
⎡ kJ ⎤
hˆ2,rev = 2391.0 ⎢ ⎥
⎣ kg ⎦
Also, from the steam tables,
⎡ kJ ⎤
hˆ1 = 3373.6 ⎢ ⎥ (500 ºC, 10 MPa)
⎣ kg ⎦
61
The reversible work is calculated as:
(W& S )rev = hˆ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎡ kJ ⎤
− hˆ1 = 2391.0 ⎢ ⎥ − 3373.6 ⎢ ⎥ = −982.6 ⎢ ⎥
2
m& 1 ⎣ kg ⎦ ⎣ kg ⎦ ⎣ kg ⎦
and the actual work as
(W& S )actual =η
(W& S )rev = −835 ⎡ kJ ⎤
m& 1 m& 1 ⎢ kg ⎥
⎣ ⎦
The exit temperature is calculated by determining the enthalpy of the actual exit state:
(W& S )actual ⎡ kJ ⎤
2, actual = h1 + = 2538.4 ⎢ ⎥
ˆh ˆ
m& 1 ⎣ 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:
2 1
n&1 = n& 2 + n&3 = n&1 + n&1
3 3
Now write the energy balance:
0 = n&1h1 − (n&2 h2 + n&3 h3 ) + Q& + W& S
Since the system is insulated and there is no shaft work, the energy balance can be rewritten as:
2 1
n&1h2 + n&1h3 − n&1h1 = 0
3 3
2
(h2 − h1 ) + 1 (h3 − h1 ) = 0
3 3
Substituting expressions for heat capacity A.2.2, we obtain the following expression:
( ) ( )
400 K T
2 ⎡ −3 4000 ⎤ 1 3
⎡ −3 4000 ⎤
3
R ∫ ⎢⎣3.280 + 0.593 × 10 T + T 2 ⎥⎦ dT + 3 R ∫ ⎢⎣3.280 + 0.593 × 10 T + T 2 ⎥⎦ dT = 0
300 K 300 K
Solving, we find
T3 = 100.6 K
Now set up an entropy balance for the process. The minimum pressure is required for a
reversible process.
2 1
n&1s2 + n&1s3 − n&1s1 = 0
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 ⎞⎤

s 2 − s1 = R ⎢ ∫ ⎢
⎢
(
+ 0.593 × 10 − 3 +)4000 ⎤
3 ⎥
dT − ln ⎜⎜ ⎟⎟⎥
⎣300 K ⎣ T T ⎦ ⎝ P1 ⎠⎥⎦
⎡100.6 K ⎡ 3.280 ⎛ 1bar ⎞⎤
s3 − s1 = R ⎢ ∫ ⎢
⎢
(
+ 0.593 ×10 − 3 + )
4000 ⎤
3 ⎥
dT − ln ⎜⎜ ⎟⎟⎥
⎣ 300 K ⎣ T T ⎦ ⎝ P1 ⎠⎥⎦
63
Substitute these expressions into the entropy balance and solve for P1:
P1 = 1.85 bar
64
3.30
A schematic of the process is illustrated below:
reversible Tsurr = 25 oC
Psurr = 1 bar
Pure H 2O
P2 = 20 bar
Pure H2O
T 2 = ? oC
P1 = 60 bar
m = 5 kg
T1 = 540 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 ⎤
sˆ1 = 6.999 ⎢ ⎥ (540 ºC, 60 bar)
⎣ kg ⋅ K ⎦
⎡ kJ ⎤
∴ sˆ2 = 6.999 ⎢ ⎥ (20 bar)
⎣ kg ⋅ K ⎦
The pressure and entropy of state 2 can be used to back out T2 from the steam tables.
T2 = 362.5 º 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
∆U = m(uˆ 2 − uˆ1 ) = W
From the steam tables,
⎡ kJ ⎤
uˆ2 = 2881.15 ⎢ ⎥ (362.5 ºC, 20 bar)
⎣ kg ⎦
65
⎡ kJ ⎤
uˆ1 = 3156.12 ⎢ ⎥ (540 ºC, 60 bar)
⎣ kg ⎦
Hence,
⎛ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞
W = (5 [kg ])⎜⎜ 2881.15 ⎢ ⎥ − 3156.12 ⎢ ⎥ ⎟⎟ = −1373 [kJ ]
⎝ ⎣ kg ⎦ ⎣ kg ⎦ ⎠
(d)
The specific volume can be found in the steam tables
⎡ m3 ⎤
vˆ2 = 0.14173 ⎢ ⎥
⎢⎣ kg ⎥⎦
Therefore,
⎛
⎜
⎡ m3 ⎤ ⎞
V2 = (5 [kg ])⎜ 0.14173 ⎢ [ ]
⎥ ⎟ = 0.709 m
⎟
3
⎝ ⎢⎣ kg ⎥⎦ ⎠
66
3.31
A schematic of the process is shown below:
very tiny Tsurr = 25 oC
leak hole
Psurr = 1 bar
Pure H2O Pure H2O
P1 = 60 bar P2 = 20 bar
T1 = 540 oC T ' 2 = ? oC
m = 5 kg
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 Problem 3.30
T surr = 25 oC
Psurr = 1 bar reversible Tsurr = 25 oC
Psurr = 1 bar
latches
Pure H2O
Pure H 2O
Pure H2O irreversible P2 = 20 bar P2 = 20 bar
Pure H2O
P1 = 60 bar T ' 2 = ? oC T 2 = ? oC
P1 = 60 bar
T1 = 540 oC m = 5 kg m = 5 kg
T1 = 540 oC
m = 5 kg
m = 5 kg
well-insulated
67
3.32
(a)
Consider the tank as the system.
Mass balance
dm
= m& in − m& out = m& in
dt
Separating variables and integrating:

m2 t
∫ dm = ∫ m& in dt
m1 0
or
t
m2 − m1 = ∫ m& in dt
0
Energy balance
Since the potential and kinetic energy effects can be neglected, the open system, unsteady state
energy balance is
⎛ dU ⎞
⎜ ⎟ = ∑ m& out hout − ∑ m& in hin + Q& + W& 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 ⎞
⎜ ⎟ = m& in hin
⎝ dt ⎠ sys
The following math is performed
U2 t t
∫ dU = ∫ m&
U1 =0 0
h dt = hin ∫ m& in dt
in in
0
U 2 − = m2uˆ 2 = m2 hîn
where the results of the mass balance were used. Thus,
uˆ 2 = hîn
68
⎡ kJ ⎤
hîn = 3456.5 ⎢ ⎥ (3 MPa, 773 K)
⎣ kg ⎦
Now the water in the tank is constrained. From the steam tables:
⎡ kJ ⎤
sˆ2 = 7.743 ⎢ ⎥
⎣ kg ⋅ K ⎦ ⎛ ⎡ kJ ⎤ ⎞
⎜ 3 MPa, uˆ 2 = 3456.5 ⎢ ⎥ ⎟
⎡m 3⎤ ⎜ ⎟
⎝ ⎣ kg ⎦ ⎠
vˆ2 = 0.14749 ⎢ ⎥
⎣⎢ kg ⎦⎥
Compute the change in entropy. An entropy balance gives:
⎛ dS ⎞ ⎛ dS ⎞
⎜ ⎟ = ⎜ ⎟ − m& in sin
⎝ dt ⎠ univ ⎝ dt ⎠ sys
Integrating with sin constant
t
∆S univ = m2 sˆ2 − sîn ∫ m& in dt = m2 (sˆ2 − sîn )
0
⎡ kJ ⎤
sîn = 7.2337 ⎢ ⎥ (3 MPa, 773 K)
⎣ kg ⋅ K ⎦
Therefore,
⎛ ⎞
⎜ ⎟
⎜ 0.05 m 3 ⎟⎛ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞
⎟ = 0.173 ⎡ ⎤
kJ
∆S univ = ⎜ ⎟⎜ 7.743 ⎢
⎜ ⎥ − 7.2337 ⎢ ⎥ ⎟ ⎢ ⎥
⎜ ⎡ m 3 ⎤ ⎟⎝ ⎣ kg ⋅ K ⎦ ⎣ kg ⋅ K ⎦ ⎠ ⎣K⎦
⎜ 0.14749 ⎢ ⎥⎟
⎜ ⎢ kg ⎥⎦ ⎟⎠
⎝ ⎣
(b)
If it tank sits in storage for a long time and equilibrates to a final temperature of 20 ºC, 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 ºC. The change in
entropy between state 2 and state 3 is given by the following equation
69
∆S univ = m2 (sˆ3 − sˆ2 ) +
Qsurr
T
Let the subscript “3” designate the final state of the water when it has reached a temperature of
20 ºC. First, find quality of the water. From the steam tables:
⎡ m3 ⎤
ˆv3sat
, l = 0.001002 ⎢ kg ⎥
⎣⎢ ⎦⎥
(sat. water at 20 ºC)
⎡ m3 ⎤
vˆ3sat
,v = 57 . 79 ⎢ ⎥
⎣⎢ kg ⎦⎥
Calculate the quality as follows:
vˆ3 = vˆ2 = (1 − x )vˆ3sat ˆ sat

, l + xv3, v
⎡ m3 ⎤ ⎛ ⎡ m3 ⎤ ⎞ ⎛ ⎡ m3 ⎤ ⎞
0.14749 ⎢ ⎥ = (1 − x )⎜⎜ 0.001002 ⎢ ⎥ ⎟⎟ + x⎜⎜ 57.79 ⎢ ⎥ ⎟⎟
⎣ kg ⎦ ⎝ ⎣ kg ⎦ ⎠ ⎝ ⎣ kg ⎦ ⎠
x = 0.0025
Now calculate the entropy of state 3
sˆ3 = (1 − x )sˆ3sat ˆ sat

, l + xs3, v
Substitute values from the steam tables:
⎛ ⎡ kJ ⎤ ⎞ ⎛ ⎡ kJ ⎤ ⎞
sˆ3 = (1 − 0.0025)⎜⎜ 0.2966 ⎟
⎢ kg ⋅ K ⎥ ⎟ + 0.0025⎜
⎜ 8.6671 ⎢ kg ⋅ K ⎥ ⎟⎟
⎝ ⎣ ⎦⎠ ⎝ ⎣ ⎦⎠
⎡ kJ ⎤
sˆ3 = 0.3175 ⎢ ⎥
⎣ kg ⋅ K ⎦
Now calculate the amount of heat transferred to the surroundings:
Q surr = −Q = − m2 (uˆ 3 − uˆ 2 )
Calculate the internal energy of state 3:
uˆ 3 = (1 − x )uˆ 3sat ˆ sat

,l + xu 3,v
Substituting values from the steam tables:
70
⎡ kJ ⎤
uˆ 3 = 89.74 ⎢ ⎥
⎣ kg ⎦
Therefore,
⎛ ⎞
⎜ ⎟
⎜ 0.05 m 3 ⎟⎛ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞
Q surr = −⎜ ⎟⎜ 89.74 ⎢ ⎥ − 3456.5 ⎢ ⎥ ⎟ = 1141 [kJ ]
⎜ ⎡ m 3 ⎤ ⎟⎜⎝ ⎣ kg ⎦
⎟
⎣ kg ⎦ ⎠
⎜ 0 . 14749 ⎢ ⎥⎟
⎜ ⎟
⎝ ⎣⎢ kg ⎦⎥ ⎠
Now calculate the change in entropy of the universe
⎛ ⎞
⎜ ⎟
⎜ 0.05 m 3
⎟⎛ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞ 1141 [kJ ]
∆S univ =⎜ ⎜ ⎢ kg ⋅ K ⎥ − ⎢ kg ⋅ K ⎥ ⎟⎟ + 293 K
3 ⎟⎜
0 .3175 7 . 743
⎡
⎜ 0.14749 ⎢ ⎥ ⎟⎝
m ⎤ ⎣ ⎦ ⎣ ⎦⎠
⎜ ⎟
⎝ ⎣ ⎦⎠
kg
⎡ kJ ⎤
∆S univ = 1.38 ⎢ ⎥
⎣K⎦
The entropy change for both processes can be fount by adding together the entropy change from
Part (a) and Part (b):
(∆S univ )(a) and (b) = 1.55⎡⎢ kJ ⎤⎥

⎣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
Mass balance
dm
= m& in − m& out = −m& out
dt
Separating variables and integrating:

m2 t
∫ dm = −∫ m&
m1 0
out dt
or
t
m2 − m1 = − ∫ m& out dt
0
Entropy Balance:
⎛ dS ⎞ Q& ⎛ dS ⎞ Q&
∆S&univ = ⎜ ⎟ + m& out sout + surr = ⎜ ⎟ + m& out sout −
⎝ dt ⎠ sys Tsurr ⎝ dt ⎠ sys Tsurr
Integrating with sout constant
∆Suniv = m2 s2 − m1s1 − (m2 − m1 )sout −

Q
(1)
Tsurr
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
Q
∆Suniv = m1 ( s 2 − s1 ) − (2)
Tsurr
Energy Balance to find Q :
⎛ dU ⎞
⎜ ⎟ = − m& out hôut + Q&
⎝ dt ⎠ sys
Integrating
∫ dU = ∫ [ ]
m 2 uˆ 2 t t t
− m& out hôut + Q& dt = −hôut ∫ m& out dt + ∫ Q& dt
m1uˆ1 0 0 0
Substituting in the mass balance and solving for Q
Q = m 2 uˆ 2 − m 1 uˆ 1 − (m 2 − m 1 )hˆ 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
m1 = 1 =
0.01 m 3 [ ]
= 0.196 [kg ]
V
and m2 = 2 =
[ ]
0.01 m 3
= 0.0785 [kg ]
v1 ⎡ m3 ⎤ v2 ⎡ m3 ⎤
0.051 ⎢ ⎥ 0.1274 ⎢ ⎥
⎣⎢ kg ⎦⎥ ⎣⎢ 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 ⎤ ⎡ kJ ⎤
u 2 = 2595.3 ⎢ ⎥ and hout = 2793.2 ⎢ ⎥
⎣ kg ⎦ ⎣ kg ⎦
Plugging in:
Q = m2uˆ2 − m1uˆ1 − (m2 − m1 )hôut = 228 [kJ ]
Back into Equation 2

⎡ kJ ⎤
228 ⎢ ⎥
⎛ ⎡ kg ⎤ ⎞⎛ ⎡ kJ ⎤ ⎞ ⎣ s ⎦ =0
= ⎜⎜ 0.196 ⎢ ⎥ ⎟⎟⎜⎜ (6.4323 − 3.9715) ⎢
Q
∆S univ = m1 ( s 2 − s1 ) − ⎥ ⎟−
⎟
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 Process V2 = 10 m3
P1 = 10 bar P2 = ?
T1 = 1000 K Work out T2 = ?
Q=0
State 1 State 2
Solving for the number of moles:
PV
n = 1 1 = 120.3 mol
RT1
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
5/ 2
⎛ T2 ⎞ P2 nRT2
⎜⎜ ⎟⎟ = =
⎝ T1 ⎠ P1 V2 P1
Solving for T2 gives
2/3
⎡ nR(T )5 / 2 ⎤
T2 = ⎢ 1
⎥ = 215 K
⎢⎣ V2 P1 ⎥⎦
An energy balance on this closed system gives:
T2 T2
∆U = Q + W = W = n ∫ c v dT = n ∫ (cP − R )dT
T1 T1
Solving for work, we get
3
W = n R(T2 − T1 ) = −1.18 ×10 J
6
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,
298.15 K
n = 1− = 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 P (bar) T (ºC)

1 30 500
2 0.1
3
4
From our knowledge of ideal Rankine cycles, the table can be expanded as follows
State Thermodynamic P (bar) T (ºC)

State
1 Superheated Steam 30 500
2 Sat. Liq. and Vapor 0.1
3 Sat. Liquid 0.1
4 Subcooled Liquid 30
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
sˆ1 = sˆ2
and
(
W& s = m& hˆ2 − hˆ1 )
⎡ kJ ⎤
sˆ1 = 7.2337 ⎢ ⎥ (500 ºC, 30 bar)
⎣ kg ⋅ K ⎦
⎡ kJ ⎤
sˆ2l = 0.6492 ⎢ ⎥
⎣ kg ⋅ K ⎦
(sat. H2O at 0.1 bar)
⎡ kJ ⎤
sˆ2v = 8.1501 ⎢ ⎥
⎣ kg ⋅ K ⎦
⎡ kJ ⎤
hˆ1 = 3456.5 ⎢ ⎥ (500 ºC, 30 bar)
⎣ kg ⎦
⎡ kJ ⎤
hˆ2l = 191.81 ⎢ ⎥
⎣ kg ⎦
(sat. H2O at 0.1 bar)
⎡ kJ ⎤
hˆ2v = 2584.6 ⎢ ⎥
⎣ kg ⎦
77
The quality of the water can be calculated as follows
sˆ1 = (1 − x) sˆ2l + xsˆ2v
By substituting the steam table data, we find
x = 0.878
Now the quality can be used for the following expression
hˆ2 = (1 − x)hˆ2l + xhˆ2v
Substituting the steam table data and the quality calculated above, we get
⎡ kJ ⎤
hˆ2 = 2292.7 ⎢ ⎥
⎣ kg ⎦
Therefore,
⎛ ⎡ kg ⎤ ⎞⎛ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞
W& s = ⎜⎜100 ⎢ ⎥ ⎟⎟⎜⎜ 2292.7 ⎢ ⎥ − 3456.5 ⎢ ⎥ ⎟⎟ = −116.38 [MW ]
⎝ ⎣ s ⎦ ⎠⎝ ⎣ kg ⎦ ⎣ kg ⎦ ⎠
At state 3,
⎡ kJ ⎤
hˆ3 = 191.81 ⎢ ⎥
⎣ kg ⎦
(sat. H2O(l) at 0.1 bar)
⎡ m3 ⎤
ˆv3 = 0.001010 ⎢ ⎥
⎣⎢ kg ⎦⎥
Therefore,
( )
Q& C = m& hˆ3 − hˆ2 = −210.09 [MW ]
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
W& c = m& vˆ3 (P4 − P3 )

⎡ kg ⎤⎛ ⎡ m3 ⎤ ⎞
( )
W& c = 100 ⎢ ⎥⎜⎜ 0.00101 ⎢ ⎥ ⎟⎟ 30 × 105 − 0.1 × 105 [Pa ] = 3.02 × 10 5 [W ] = 0.302 [MW ]
⎣ s ⎦⎝ ⎣ kg ⎦ ⎠
78
Now we find the rate of heat transfer for the evaporator. For the entire Rankine cycle, Equation
3.84 gives
Q& net + W& net = Q& C + Q& H + W& s + W&C = 0
We have
Q& H = −W& s − W&C − Q& C
Using the values calculated above:
Q& H = 326.2 [MW ]
Equation 3.84:
W& net = W& S − W&C

W& net = 116.08 [MW ]
The efficiency can be calculated with Equation 3.82
W& 116.08 [MW ]

η = &net = = 0.356
QH 326.02 [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
T T
1new
1
wnet wnet
4 4new
2new
3
3new 2new
s s
2 stage turbine with reheat

increase the boiler pressure
Turbine 1
1 Turbine 2
T T
1 3
6
2
wnet wnet
4
4
3 2 5
s s
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
Ws Ws
turbine Tur-
1 bine
1 2
2
Fuel
Air
4
QH 3
Boiler QC cooling
water
6
condenser
5
Wc
compressor
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
State P (bar) T (ºC)

1 100 500
2 1
3
4
State Thermodynamic P (bar) T (ºC)

State
1 Superheated Steam 100 500
2 Sat. Liq. and Vapor 1
3 Sat. Liquid 1
4 Subcooled Liquid 100
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
sˆ1 = sˆ2
⎡ kJ ⎤
sˆ1 = 6.5965 ⎢ ⎥ (500 ºC, 100 bar)
⎣ kg ⋅ K ⎦
⎡ kJ ⎤
sˆ2l = 1.3025 ⎢ ⎥
⎣ kg ⋅ K ⎦
(sat. H2O at 1 bar)
⎡ kJ ⎤
sˆ2v = 7.3593 ⎢ ⎥
⎣ kg ⋅ K ⎦
The quality of the water can be calculated as follows
sˆ1 = (1 − x) sˆ2l + xsˆ2v
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:
hˆ4 = hˆ3 + vˆl (P4 − P3 )
⎡ m3 ⎤
where vl = v3 = 0.001043 ⎢
ˆ ˆ ⎥ since specific volume of liquids are insensitive to pressure
⎣⎢ kg ⎦⎥
changes. From the steam tables:
State 1 2 3 4
ĥ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎡ kJ ⎤
3240.8 ⎢ ⎥ 2391.0 ⎢ ⎥ 417.44 ⎢ ⎥ 427.8 ⎢ ⎥
⎣ kg ⎦ ⎣ kg ⎦ ⎣ kg ⎦ ⎣ kg ⎦
Note: hˆ2 = (1 − x)hˆ2l + xhˆ2v
Equation 3.84:
W& net = Q& H − Q& C
Therefore,
( ) ( ) [( ) (
W& net = m& hˆ1 − hˆ4 + m& hˆ3 − hˆ2 = m& hˆ1 − hˆ4 + hˆ3 − hˆ2 )]
and
W& net 100 ×103 [kW ]

m& =
[(hˆ1 − hˆ4 )+ (hˆ3 − hˆ2 )] =
⎡⎛ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞ ⎛ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞⎤
⎢⎜⎜ 3240.8 ⎢ ⎥ − 417.5 ⎢ ⎥ ⎟⎟ + ⎜⎜ 427.8 ⎢ ⎥ − 2391.0 ⎢ ⎥ ⎟⎟⎥
⎢⎣⎝ ⎣ kg ⎦ ⎣ kg ⎦ ⎠ ⎝ ⎣ kg ⎦ ⎣ kg ⎦ ⎠⎥⎦
⎡ kg ⎤
m& = 116.3 ⎢ ⎥
⎣s ⎦
Now consider the non-ideal turbine and compressor. Use the definition of isentropic
efficiencies:
ηturbine = &
(W& s )actual
(Ws )reversible
∴ (W& S )actual = ηturbine (W& S )reversible = ηturbine (m& )(hˆ2 − hˆ1 )reversible
83
ηcompressor =
(W&C )reversible
(W&C )actual
(W&C )reversible m& (hˆ4 − hˆ3 )reversible
∴ (W&C )actual = =
ηcompressor ηcompressor
Equation 3.84 is used to find the mass flow rate
W& net = W& s − W&C

⎡
W& net = m& ⎢ηturbine hˆ2 − hˆ1 +
( )
hˆ4 − hˆ3 reversible ⎤
⎥
⎢⎣ reversible ηcompressor ⎥⎦
Substituting the enthalpy values from the table shown above and the efficiency values gives
⎡ kg ⎤
m& = 147 ⎢ ⎥
⎣ 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
State Thermodynamic P (MPa)

State
1 Sat. Vapor 1.7
2 0.7
3
4

State
1 Sat. Vapor 1.7
2 Sat. Liq. And Vapor 0.7
3 Sat. Liquid 0.7
4 Subcooled Liquid 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
hˆ2 = (1 − x)hˆ2l + xhˆ2v

hˆ4 = hˆ3 + vˆl (P4 − P3 ) = hˆ3 + vˆ3 (P4 − P3 )
To find x, use the fact that the turbine is isentropic.
sˆ1 = sˆ2
sˆ1 = (1 − x) sˆ2l + xsˆ2v
From the NIST website:
⎡ J ⎤
s1 = 146.38 ⎢ (sat. vapor at 1.7 MPa)
⎣ mol ⋅ K ⎥⎦
⎡ J ⎤
s2l = 90.45 ⎢
⎣ mol ⋅ K ⎥⎦
(sat. mixture at 0.7 MPa)
⎡ J ⎤
s2v = 150.07 ⎢
⎣ mol ⋅ K ⎥⎦
By substituting the above values into the entropy relationship, we find
85
x = 0.938
Also, from the NIST website:
⎡ J ⎤
h1 = 36046 ⎢ (sat. vapor at 1.7 MPa)
⎣ mol ⎥⎦
⎡ J ⎤
h2l = 18416 ⎢
⎣ mol ⎥⎦
(sat. mixture at 0.7 MPa)
⎡ J ⎤
h2v = 35353 ⎢
⎣ mol ⎥⎦
⎡ J ⎤
h3 = 18416 ⎢
⎣ mol ⎥⎦
(sat. liquid at 0.7 MPa)
−5 m
⎡ 3⎤
v3 = 6.954 ×10 ⎢ ⎥
⎣⎢ mol ⎦⎥
Substituting these values into the expression for h4 and h2 yields
⎡ J ⎤
h2 = 34302.9 ⎢ ⎥
⎣ mol ⎦
⎡ J ⎤
h4 = 18485.5 ⎢
⎣ mol ⎥⎦
h2 − h1 − (h4 − h3 )
η rankine =
h1 − h4
⎡ J ⎤ ⎡ J ⎤ ⎛ ⎡ J ⎤ ⎡ J ⎤⎞
34302.9 ⎢ ⎥ − 36046 ⎢ ⎥ − ⎜⎜18485.5 ⎢ ⎥ − 18416 ⎢ ⎟⎟
⎣ mol ⎦ ⎣ mol ⎦ ⎝ ⎣ mol ⎦ ⎣ mol ⎥⎦ ⎠
∴η rankine =
⎡ J ⎤ ⎡ J ⎤
36046 ⎢ ⎥ − 18485.5 ⎢
⎣ mol ⎦ ⎣ mol ⎥⎦
η 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

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.
Q& C = n& (h2 − h1 )
which upon combination with Equation 3.89 gives
Q& C = n& (h2 − h4 )
⎡ kJ ⎤
h2 = 39.295 ⎢ (sat. vapor at 0.12 MPa)
⎣ mol ⎥⎦
⎡ kJ ⎤
h4 = 24.181 ⎢ ⎥ (sat. liquid at 0.7 MPa)
⎣ 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:
W&C = n& (h3 − h2 )
s 2 = s3
87
⎡ J ⎤
s3 = s2 (sat. vapor at 0.12 MPa ) = 177.89 ⎢
⎣ mol ⋅ K ⎥⎦
Now, state 3 is constrained.
⎡ kJ ⎤ ⎛ ⎡ J ⎤⎞
h3 = 43.031 ⎢ ⎜⎜ 0.7 MPa, s3 = 177.89 ⎢ ⎥ ⎟⎟
⎣ mol ⎥⎦ ⎝ ⎣ mol ⋅ K ⎦⎠
Therefore,
⎛ ⎡ mol ⎤ ⎞⎛ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞
W&C = ⎜⎜ 0.5 ⎢ ⎥ ⎟⎟⎜⎜ 43.031 ⎢ ⎥ − 39.295 ⎢ ⎟⎟ = 1.87 [kW ]
⎝ ⎣ s ⎦ ⎠⎝ ⎣ mol ⎦ ⎣ mol ⎥⎦ ⎠
(c)
Equation 3.90 states:
⎡ kJ ⎤ ⎡ kJ ⎤
39.295 ⎢ − 24.181
h −h h −h
COP = 2 1 = 2 4 = ⎣ mol ⎥⎦ ⎢⎣ mol ⎥⎦
= 4.05
h3 − h2 h3 − h2 ⎡ kJ ⎤ ⎡ kJ ⎤
43.031 ⎢ − 39.295 ⎢
⎣ 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

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
Q& C h2 − h1
COP = =
W& C 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 ⎢ (sat. vapor at 0.12 MPa)
⎣ mol ⎥⎦
For the process between state 2 and state 3,
s 2 = s3
⎡ J ⎤
s3 = s 2 = 177.89 ⎢ (sat. vapor at 0.12 MPa)
⎣ mol ⋅ K ⎥⎦
Now, state 3 is constrained.
⎡ kJ ⎤ ⎛ ⎡ J ⎤⎞
h3 = 43.031 ⎢ ⎜⎜ 0.7 MPa, s3 = 177.89 ⎢ ⎥ ⎟⎟
⎣ mol ⎥⎦ ⎝ ⎣ mol ⋅ K ⎦ ⎠
The process between state 4 and state 1 is also isentropic.
⎡ J ⎤
s1 = s 4 = 115.09 ⎢ (sat. liquid at 0.7 MPa)
⎣ mol ⋅ K ⎥⎦
The quality of the R134a can be calculated as follows
89
s1 = (1 − x )s1l + xs1v
where
⎡ J ⎤
s1l = 90.649 ⎢ (sat. R134a(l) at 0.12 MPa)
⎣ mol ⋅ K ⎥⎦
⎡ J ⎤
s1v = 177.89 ⎢ ⎥ (sat. R134a(v) at 0.12 MPa)
⎣ mol ⋅ K ⎦
Therefore,
⎡ J ⎤ ⎛ ⎡ J ⎤⎞ ⎛ ⎡ J ⎤⎞
115.09 ⎢ ⎥ = (1 − x )⎜⎜ 90.649 ⎢ ⎥ ⎟⎟ + x⎜⎜177.89 ⎢ ⎟⎟
⎣ mol ⋅ K ⎦ ⎝ ⎣ mol ⋅ K ⎦ ⎠ ⎝ ⎣ mol ⋅ K ⎥⎦ ⎠
∴ x = 0.280
Using the quality of R134a, the enthalpy of state 1 can be calculated as follows
h1 = (1 − x )h1l + xh1v
⎡ kJ ⎤
h1l = 17.412 ⎢ (sat. R134a(l) at 0.12 MPa)
⎣ mol ⎥⎦
⎡ kJ ⎤
h1v = 39.295 ⎢ ⎥ (sat. R134a(v) at 0.12 MPa)
⎣ mol ⎦
Therefore,
⎛ ⎡ kJ ⎤ ⎞ ⎛ ⎡ kJ ⎤ ⎞
h1 = (1 − 0.28)⎜⎜17.412 ⎢ ⎥ ⎟⎟ + 0.28⎜⎜ 39.295 ⎢ ⎟⎟
⎝ ⎣ mol ⎦ ⎠ ⎝ ⎣ 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
COP = 2 1 = ⎣ mol ⎦ ⎣ mol ⎥⎦ = 4.97
h3 − h2 ⎡ kJ ⎤ ⎡ kJ ⎤
43.031 ⎢ ⎥ − 39.295 ⎢
⎣ mol ⎦ ⎣ mol ⎥⎦
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 = Q& C , h = Q&
Written in terms of enthalpy, the equation is
n& c (h8 − h7 ) = − n& h (h2 − h1 )
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 ⎢ (sat. R134 liquid at 0.7 MPa)
⎣ mol ⎥⎦
⎡ J ⎤
h2 = 40967 ⎢ (sat. R134 vapor at 0.35 MPa)
⎣ mol ⎥⎦
⎡ J ⎤ ⎡ J ⎤
h7 = 41510 ⎢ (R134 vapor at 0.35 MPa with s = 177.89 ⎢ )
⎣ mol ⎥⎦ ⎣ mol ⋅ K ⎥⎦
⎡ J ⎤
⎣ mol ⎥⎦
Now the flow rate can be calculated:
⎛ ⎡ J ⎤ ⎡ J ⎤⎞
− (0.5 [mol/s])⎜⎜ 40967 ⎢ ⎥ − 24181 ⎢ ⎟⎟
⎝ ⎣ mol ⎦ ⎣ mol ⎥⎦ ⎠
n& c =
⎛ ⎡ J ⎤ ⎡ J ⎤⎞
⎜⎜ 21099 ⎢ ⎥ − 41510 ⎢ ⎟⎟
⎝ ⎣ mol ⎦ ⎣ mol ⎥⎦ ⎠
⎡ mol ⎤
n&c = 0.411 ⎢
⎣ s ⎥⎦
92
(b)
Performing an energy balance we find
Q& C = n& c (h6 − h5 )
We can also use the following relationship
⎡ J ⎤
h5 = h8 = 21099 ⎢
⎣ mol ⎥⎦
⎡ J ⎤
⎣ mol ⎥⎦
Therefore,
⎛ ⎡ mol ⎤ ⎞⎛ ⎡ J ⎤ ⎡ J ⎤⎞
Q& C = ⎜⎜ 0.411 ⎢ ⎥ ⎟⎟⎜⎜ 39295 ⎢ ⎥ − 21099 ⎢ ⎟⎟ = 7.48 [kW ]
⎝ ⎣ s ⎦ ⎠⎝ ⎣ mol ⎦ ⎣ mol ⎥⎦ ⎠
(c)
The power input is calculated as follows:
W&C , total = W&C , c + W&C , h
where
W&C , c = n&c (h7 − h6 )

W&C , h = n& h (h3 − h2 )
We have all of the required enthalpies except h3. State 3 is constrained because
⎡ J ⎤
s3 = s 2 = 175.95⎢ (sat. R134a vapor at 0.35 MPa)
⎣ mol ⋅ K ⎥⎦
P3 = 0.7 MPa
⎡ J ⎤ ⎡ J ⎤
h3 = 42428 ⎢ (R134a vapor at 0.7 MPa with s = 175.95⎢ )
⎣ mol ⎥⎦ ⎣ mol ⋅ K ⎥⎦
Now compute the power for each unit:
93
⎛ ⎡ J ⎤ ⎡ J ⎤⎞ ⎛ ⎡ J ⎤ ⎡ J ⎤⎞
W&C , total = 0.411 [mol/s]⎜⎜ 41510 ⎢ ⎥ − 39295 ⎢ ⎥ ⎟⎟ + 0.5 [mol/s]⎜⎜ 42428 ⎢ ⎥ − 40967 ⎢ ⎟⎟
⎝ ⎣ mol ⎦ ⎣ mol ⎦ ⎠ ⎝ ⎣ mol ⎦ ⎣ mol ⎥⎦ ⎠
W& C , total = 1.64 [kW ]
(d)
The coefficient of performance is calculated using the following equation:
Q& C 7.48 kW
COP = = = 4.56
W&C , total 1.64 kW
(e)
The COP for the cascade is 4.56, while the COP is 4.05 in Problem 3.40. The cascade system’s
COP is 12.6% greater.
94
3.43
One design follows; your design may differ:
In order to cool a system to -5 ºC, the temperature of the fluid must be colder than -5 ºC so that
heat transfer will occur. We arbitrarily specify that the working fluid evaporates at -10 ºC.
Similarly, in order to eject heat to the 20 ºC reservoir, the fluid must condense at a temperature
greater than 20 ºC. Arbitrarily, we choose 25 ºC. One possible refrigeration cycle is presented
below.
Ý
valve
T 3
1
evaporator QH
4
refrigerated 4
unit at -5 C QC
QH 20 C
reservoir
2
1 2
condenser QC
3
Wc s
compressor
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
P1 = P2 = 0.201 MPa (Tsat = -10 ºC)

P3 = P4 = 0.665 MPa (Tsat = 25 ºC)
(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.
Q& C = n& (h2 − h1 )
We can get h2 from the thermodynamic tables for saturated R134a. In order to find h1, we can
use the following relationship:
h1 = h4
⎡ J ⎤
⎣ mol ⎥⎦
95
⎡ J ⎤
⎣ mol ⎥⎦
Now, calculate the required flow rate of R134a.
Q& C 20,000 [J/s]

n& = =
(h2 − h1 ) ⎛ ⎡ J ⎤ ⎡ J ⎤⎞
⎜⎜ 40064 ⎢ ⎥ − 23931 ⎢ ⎟⎟
⎝ ⎣ mol ⎦ ⎣ mol ⎥⎦ ⎠
⎡ mol ⎤
n& = 1.24 ⎢
⎣ s ⎥⎦
96
3.44
The schematic of the process and the corresponding Ts is presented below
T = 5 oC
valve
Fridge 6
T
2 QC,R 1
valve 1 QH
evaporator
Wc
3 6
QC,R
5 oC
T = -15 oC Freezer evaporator QH high T 2 3
QC,F reservoir QC,F
4 -15 oC 4 5
5 condenser
Wc s
compressor
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 doesn’t state what temperature the fluid condenses at. Therefore,
we can assume the temperature is 25 ºC. By using information in the Ts diagram and from the
NIST website, we find
P1 = P2 = 0.34966 MPa (T1=T2=Tsat = 5 ºC)

P3 = P4 = 0.16394 MPa (T3=T4=Tsat = -15 ºC)
P5 = P6 = 0.66538 MPa (T6 = 25 ºC)
Before solving for additional pressures and temperatures, we will list the known temperatures
and pressures.
State Temperature (ºC) Pressure (MPa)

1 5 0.24334
2 5 0.24334
3 -15 0.16394
4 -15 0.16394
5 25 0.66538
6 25 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 = Q& C , 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
⎡ 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 ⎤
39755 ⎢ ⎥ + 23931 ⎢
h2 = h3 = ⎣ mol ⎦ ⎣ mol ⎥⎦ = 31843 ⎡ J ⎤
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:
h1 = (1 − x1 )h1sat sat
, l + x1h1, v
h2 = (1 − x2 )h2sat sat
, l + x2 h2, v
h3 = (1 − x3 )h3sat sat
, l + x3 h3, v
From the NIST website,
98
⎡ J ⎤ ⎡ J ⎤
h1sat
, l = 21095 ⎢ mol ⎥ h1sat
, v = 40965 ⎢ mol ⎥
⎣ ⎦ ⎣ ⎦
⎡ J ⎤ ⎡ J ⎤
h2sat
, l = 21095 ⎢ mol ⎥ h2sat
, v = 40965 ⎢ mol ⎥
⎣ ⎦ ⎣ ⎦
⎡ J ⎤ ⎡ J ⎤
h3sat
, l = 18380 ⎢ mol ⎥ h3sat
, 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:
Temperature Pressure Liquid Vapor

State Phases
(ºC) (MPa) Composition Composition
Saturated Liquid
1 5 0.24334 0.857 0.143
and Vapor
Saturated Liquid
2 5 0.24334 0.459 0.541
and Vapor
Saturated Liquid
3 -15 0.16394 0.37 0.630
and Vapor
4 -15 0.16394 Saturated Vapor 0 1
Superheated
5 25 0.66538 0 1
Vapor
6 25 0.66538 Saturated Liquid 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
QH
QC
1 4
(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:
qC qC
COP = = = 0.11
wC ,total 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 ∆h ºf (kJ/mol) ∆g ºf (kJ/mol)

Cu2O (s) -170.71 -147.88
O2 (g) 0 0
CuO (s) -156.06 -128.29
The data listed above were used to create the next table using
∆h ºf − ∆g ºf
∆s ºf =
T
Species ∆s ºf (kJ/mol K)
Cu2O (s) -0.0766
O2 (g) 0
CuO (s) -0.0932
Now the change in entropy of the reaction can be calculated in a method analogous to Equation
2.72
º
∆s rxn ( )
i
⎛
⎝
⎡ kJ ⎤ ⎞ ⎛
= ∑ vi ∆s ºf = −2⎜⎜ - 0.0766 ⎢ ⎥
⎡ kJ ⎤ ⎞
⎟⎟ + 4⎜⎜ - 0.0932 ⎢
⎣ mol ⋅ K ⎦ ⎠ ⎝
⎟⎟
⎣ mol ⋅ K ⎥⎦ ⎠
º ⎡ 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
P
C= = 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

Engineering and Chemical Thermodynamics: Chapter 3 Solutions

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Engineering and Chemical Thermodynamics: Chapter 3 Solutions

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Chapter 3 Solutions

Engineering and Chemical Thermodynamics

Department of Chemical Engineering

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

Using the definition of entropy,

For an ideal gas, the following can be shown

Combination of both steps yields

Equation 3.62 states

Substituting the equation for c P yields

∆S univ = ∆S sys + ∆S surr

∆S sys = m( sˆ2 − sˆ1 )

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

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

vˆ2 = (1 − x )vˆ2l , sat + xvˆ2v, sat

From the steam tables:

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

sˆ2 = (1 − x )sˆ2l , sat + xsˆ2v, sat

Now the entropy change of the system can be calculated.

To following expression is used to solve for the internal energy:

From the steam tables

The expression for internal energy yields

Qsurr 20583.77 [kJ ] ⎡ kJ ⎤

Now the change in entropy of the universe can be calculated

Since ∆Suniv > 0, this process is possible.

∆S univ = ∆S sys + ∆S surr

du = δq (neglecting PE and KE)

This can be used in the following expression for entropy

From Table A.2.3

Qsurr −Q − nCu c P (T2 − T1 ) − 2.723nCu R(T2 − T1 )

From the definition of entropy:

⎡J⎤ ⎡J⎤ ⎡J⎤

n Ac P (T2 − 373.15 K ) + n B c P (T2 − 473.15 K ) = 0

Now, calculate the change in entropy:

Substituting values, we obtain

The gas in the piston-cylinder system is ideal and c P is constant, so

From the problem statement, we know

The ideal gas law can be used to solve T1 .

Conservation of mass requires

The energy balance can be rewritten as

ncv (T2 − T1 ) = − PE (V2 − V1 )

V2 and T1 can be rewritten using the ideal gas law

Using the following values

This can be used to find V2 .

Th polytropic expression can also be manipulated to yield

Substitution of the appropriate variables provides

Now the entropy can be calculated,

Equation 3.3 states

From the steam tables

Now V2 and v2 are found as follows

Therefore, this process is irreversible.

From Equation 3.63:

Now, we can use Equation 3.65

(ii). From the steam tables:

We can get the moles of water and ice.

From Appendix A.2.3

(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,