Chapter 3 - Section A - Mathcad Solutions

−1 ⎛ d ⎞ 1 ⎛d ⎞
3.1 β = ⋅⎜ ρ κ= ⋅⎜ ρ
ρ ⎝ dT ⎠ ρ ⎝ dP ⎠
P T
At constant T, the 2nd equation can be written:

dρ ⎛ ρ2 ⎞ −6 −1
= κ ⋅ dP ln ⎜ = κ ⋅ ∆P κ := 44.18⋅ 10 ⋅ bar ρ 2 = 1.01⋅ ρ 1
ρ ⎝ ρ1 ⎠
ln ( 1.01)
∆P := ∆P = 225.2 bar P2 = 226.2⋅ bar Ans.
κ

3
cm
3.4 b := 2700⋅ bar c := 0.125⋅ P1 := 1⋅ bar P2 := 500⋅ bar
gm
V
⌠ 2
Since Work = −⎮ P dV a bit of algebra leads to
⌡V
1

P
⌠ 2 P
Work := c⋅ ⎮ dP J
⎮ P+b Work = 0.516 Ans.
⌡P gm
1

Alternatively, formal integration leads to

⎛ ⎛ P2 + b ⎞ ⎞ J
Work := c⋅ ⎜ P2 − P1 − b⋅ ln ⎜ Work = 0.516 Ans.
⎝ ⎝ P1 + b ⎠ ⎠ gm

−6 −1 −9 −2
3.5 κ = a + b⋅ P a := 3.9⋅ 10 ⋅ atm b := −0.1⋅ 10 ⋅ atm
3
P1 := 1⋅ atm P2 := 3000⋅ atm V := 1⋅ ft (assume const.)

Combine Eqs. (1.3) and (3.3) for const. T:

P
⌠ 2 3
Work := V⋅ ⎮ ( a + b⋅ P) ⋅ P dP Work = 16.65 atm⋅ ft Ans.
⌡P
1

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 3.6 β := 1.2⋅ 10− 3⋅ degC− 1
kJ
CP := 0.84⋅ M := 5⋅ kg
kg⋅ degC
3
1 m
V1 := ⋅ P := 1⋅ bar t1 := 0⋅ degC t2 := 20⋅ degC
1590 kg
With beta independent of T and with P=constant,

V2 := V1⋅ exp ⎡⎣β ⋅ ( t2 − t1)⎤⎦

dV
= β ⋅ dT ∆V := V2 − V1
V
−5 3
∆Vtotal := M⋅ ∆V ∆Vtotal = 7.638 × 10 m Ans.

Work := −P⋅ ∆Vtotal (Const. P) Work = −7.638 joule Ans.

Q := M⋅ CP⋅ ( t2 − t1) Q = 84 kJ Ans.

∆Htotal := Q ∆Htotal = 84 kJ Ans.

∆Utotal := Q + Work ∆Utotal = 83.99 kJ Ans.

3.8 7 5
P1 := 8⋅ bar P2 := 1⋅ bar T1 := 600⋅ K CP := ⋅R CV := ⋅R
2 2

(a) Constant V: W= 0 and ∆U = Q = CV⋅ ∆T

P2
T2 := T1⋅ ∆T := T2 − T1 ∆T = −525 K
P1
kJ
∆U := CV⋅ ∆T Q and ∆U = −10.91 Ans.
mol

kJ
∆H := CP⋅ ∆T ∆H = −15.28 Ans.
mol

(b) Constant T: ∆U = ∆H = 0 and Q= W

⎛ P2 ⎞ kJ
Work := R⋅ T1⋅ ln ⎜ Q and Work = −10.37 Ans.
⎝ P1 ⎠ mol

(c) Adiabatic: Q= 0 and ∆U = W = CV⋅ ∆T

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 γ −1
γ
CP ⎛ P2 ⎞
γ := T2 := T1⋅ ⎜ T2 = 331.227 K ∆T := T2 − T1
CV ⎝ P1 ⎠
∆U := CV⋅ ∆T ∆H := CP⋅ ∆T

kJ kJ
W and ∆U = −5.586 Ans. ∆H = −7.821 Ans.
mol mol

7 5
3.9 P4 := 2bar CP := R CV := R
2 2
R ⋅ T1 −3 m
3
P1 := 10bar T1 := 600K V1 := V1 = 4.988 × 10
P1 mol
R
CP
⎛ P4 ⎞
Step 41: Adiabatic T4 := T1⋅ ⎜ T4 = 378.831 K
⎝ P1 ⎠

∆U41 := CV⋅ ( T1 − T4)

3 J
∆U41 = 4.597 × 10
mol
∆H41 := CP⋅ ( T1 − T4) 3 J
∆H41 = 6.436 × 10
mol
J J
Q41 := 0 Q41 = 0
mol mol

3 J
W41 := ∆U41 W41 = 4.597 × 10
mol

R ⋅ T2 m
3
P2 := 3bar T2 := 600K V2 := V2 = 0.017
P2 mol

J J
Step 12: Isothermal ∆U12 := 0 ∆U12 = 0
mol mol
J
∆H12 := 0⋅ J
mol ∆H12 = 0
mol

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 ⎛ P2 ⎞ 3 J
Q12 := −R⋅ T1⋅ ln ⎜ Q12 = 6.006 × 10
⎝ P1 ⎠ mol

3 J
W12 := −Q12 W12 = −6.006 × 10
mol

P3⋅ V3
P3 := 2bar V3 := V2 T3 := T3 = 400 K
R

∆U23 := CV⋅ ( T3 − T2)

3 J
Step 23: Isochoric ∆U23 = −4.157 × 10
mol

∆H23 := CP⋅ ( T3 − T2)

3 J
∆H23 = −5.82 × 10
mol

Q23 := CV⋅ ( T3 − T2)

3 J
Q23 = −4.157 × 10
mol
J J
W23 := 0 W23 = 0
mol mol

R ⋅ T4 m
3
P4 = 2 bar T4 = 378.831 K V4 := V4 = 0.016
P4 mol

∆U34 := CV⋅ ( T4 − T3)

J
Step 34: Isobaric ∆U34 = −439.997
mol

∆H34 := CP⋅ ( T4 − T3)

J
∆H34 = −615.996
mol

Q34 := CP⋅ ( T4 − T3)

J
Q34 = −615.996
mol

W34 := −R⋅ ( T4 − T3)

J
W34 = 175.999
mol

3.10 For all parts of this problem: T2 = T1 and

∆U = ∆H = 0 Also Q = −Work and all that remains is

to calculate Work. Symbol V is used for total volume in this problem.

3 3
P1 := 1⋅ bar P2 := 12⋅ bar V1 := 12⋅ m V2 := 1⋅ m

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 ⎛ P2 ⎞ ⎛ P2 ⎞
(a) Work = n⋅ R⋅ T⋅ ln ⎜ Work := P1⋅ V1⋅ ln ⎜
⎝ P1 ⎠ ⎝ P1 ⎠
Work = 2982 kJ Ans.

(b) Step 1: adiabatic compression to P2

1
γ
5 ⎛ P1 ⎞ 3
γ := Vi := V1⋅ ⎜ (intermediate V) Vi = 2.702 m
3 ⎝ P2 ⎠

P 2⋅ V i − P 1⋅ V 1
W1 := W1 = 3063 kJ
γ−1

Step 2: cool at const P2 to V2

W2 := −P2⋅ ( V2 − Vi) W2 = 2042 kJ

Work := W1 + W2 Work = 5106 kJ Ans.

(c) Step 1: adiabatic compression to V2

γ
⎛ V1 ⎞
Pi := P1⋅ ⎜ (intermediate P) Pi = 62.898 bar
⎝ V2 ⎠

P i ⋅ V 2 − P 1⋅ V 1
W1 := W1 = 7635 kJ
γ−1

Step 2: No work. Work := W1 Work = 7635 kJ Ans.

(d) Step 1: heat at const V1 to P2 W1 = 0

Step 2: cool at const P2 to V2

W2 := −P2⋅ ( V2 − V1) Work := W2 Work = 13200 kJ Ans.

(e) Step 1: cool at const P1 to V2

W1 := −P1⋅ ( V2 − V1) W1 = 1100 kJ

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 Step 2: heat at const V2 to P2 W2 = 0
Ans.
Work := W1 Work = 1100 kJ

3.17 (a) No work is done; no heat is transferred.

t
∆U = ∆T = 0 T2 = T1 = 100⋅ degC Not reversible

(b) The gas is returned to its initial state by isothermal compression.

⎛ V1 ⎞
Work = n⋅ R⋅ T⋅ ln ⎜ but n⋅ R⋅ T = P2⋅ V2
⎝ V2 ⎠
3 4 3
V1 := 4⋅ m V2 := ⋅m P2 := 6⋅ bar
3

⎛ V1 ⎞
Work := P2⋅ V2⋅ ln ⎜ Work = 878.9 kJ Ans.
⎝ V2 ⎠

3.18 (a) P1 := 100⋅ kPa P2 := 500⋅ kPa T1 := 303.15⋅ K

7 5 CP
CP := ⋅R CV := ⋅R γ :=
2 2 CV

Adiabatic compression from point 1 to point 2: γ −1

γ
kJ ⎛ P2 ⎞
Q12 := 0⋅ ∆U12 = W12 = CV⋅ ∆T12 T2 := T1⋅ ⎜
mol ⎝ P1 ⎠
∆U12 := CV⋅ ( T2 − T1) ∆H12 := CP⋅ ( T2 − T1) W12 := ∆U12

kJ kJ kJ
∆U12 = 3.679 ∆H12 = 5.15 W12 = 3.679 Ans.
mol mol mol

Cool at P2 from point 2 to point 3:

T3 := T1 ∆H23 := CP⋅ ( T3 − T2) Q23 := ∆H23

∆U23 := CV⋅ ( T3 − T2) W23 := ∆U23 − Q23

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 kJ kJ
∆H23 = −5.15 ∆U23 = −3.679 Ans.
mol mol

kJ kJ
Q23 = −5.15 W23 = 1.471 Ans.
mol mol

Isothermal expansion from point 3 to point 1:

⎛ P1 ⎞
∆U31 = ∆H31 = 0 P3 := P2 W31 := R⋅ T3⋅ ln ⎜
⎝ P3 ⎠
Q31 := −W31
kJ kJ
W31 = −4.056 Q31 = 4.056 Ans.
mol mol

FOR THE CYCLE: ∆U = ∆H = 0

Q := Q12 + Q23 + Q31 Work := W12 + W23 + W31

kJ kJ
Q = −1.094 Work = 1.094
mol mol

(b) If each step that is 80% efficient accomplishes the same change of state,
all property values are unchanged, and the delta H and delta U values
are the same as in part (a). However, the Q and W values change.
W12 kJ
Step 12: W12 := W12 = 4.598
0.8 mol
kJ
Q12 := ∆U12 − W12 Q12 = −0.92
mol
W23 kJ
Step 23: W23 := W23 = 1.839
0.8 mol

kJ
Q23 := ∆U23 − W23 Q23 = −5.518
mol

kJ
Step 31: W31 := W31⋅ 0.8 W31 = −3.245
mol

Q31 := −W31 kJ
Q31 = 3.245
mol

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 FOR THE CYCLE:

Q := Q12 + Q23 + Q31 Work := W12 + W23 + W31

kJ kJ
Q = −3.192 Work = 3.192
mol mol

3.19 Here, V represents total volume.

3
P1 := 1000⋅ kPa V1 := 1⋅ m V2 := 5⋅ V1 T1 := 600⋅ K
joule CP
CP := 21⋅ CV := CP − R γ :=
mol⋅ K CV

⎛ V1 ⎞ V1
(a) Isothermal: Work = n⋅ R⋅ T1⋅ ln ⎜ P2 := P1⋅
⎝ V2 ⎠ V2

T2 := T1 T2 = 600 K P2 = 200 kPa Ans.

⎛ V1 ⎞
Work := P1⋅ V1⋅ ln ⎜ Work = −1609 kJ Ans.
⎝ V2 ⎠
γ
⎛ V1 ⎞ P2 V 2
(b) Adiabatic: P2 := P1⋅ ⎜ T2 := T1⋅ ⋅
⎝ V2 ⎠ P1 V 1

T2 = 208.96 K P2 = 69.65 kPa Ans.

P2⋅ V2 − P1⋅ V1
Work := Work = −994.4 kJ Ans,
γ−1
(c) Restrained adiabatic: Work = ∆U = −Pext⋅ ∆V

Pext := 100⋅ kPa Work := −Pext⋅ ( V2 − V1) Work = −400 kJ Ans.

P 1⋅ V 1
n := ∆U = n⋅ CV⋅ ∆T
R ⋅ T1

Work
T2 := + T1 T2 = 442.71 K Ans.
n⋅ CV
V 1 T2
P2 := P1⋅ ⋅ P2 = 147.57 kPa Ans.
V 2 T1

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 3.20 T1 := 423.15⋅ K P1 := 8⋅ bar P3 := 3⋅ bar

7 5
CP := ⋅R CV := ⋅R T2 := T1 T3 := 323.15⋅ K
2 2

kJ kJ
Step 12: ∆H12 := 0⋅ ∆U12 := 0⋅
mol mol
V1 V1 T 1 P3
If r= = Then r := ⋅ W12 := R⋅ T1⋅ ln ( r)
V2 V3 T 3 P1

kJ kJ
W12 = −2.502 Q12 := −W12 Q12 = 2.502
mol mol

∆U23 := CV⋅ ( T3 − T2)

kJ
Step 23: W23 := 0⋅
mol

Q23 := ∆U23 ∆H23 := CP⋅ ( T3 − T2)

kJ kJ kJ
Q23 = −2.079 ∆U23 = −2.079 ∆H23 = −2.91
mol mol mol

kJ
Process: Work := W12 + W23 Work = −2.502 Ans.
mol

kJ
Q := Q12 + Q23 Q = 0.424 Ans.
mol

kJ
∆H := ∆H12 + ∆H23 ∆H = −2.91 Ans.
mol

kJ
∆U := ∆U12 + ∆U23 ∆U = −2.079 Ans.
mol

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 gm 1 2
3.21 By Eq. (2.32a), unit-mass basis: molwt := 28 ∆H + ⋅ ∆u = 0
mol 2

But ∆H = CP⋅ ∆T Whence ∆T =

( 2
− u2 − u1
2
)
2⋅ CP

7 R m m
CP := ⋅ u1 := 2.5⋅ u2 := 50⋅ t1 := 150⋅ degC
2 molwt s s

2 2
u2 − u1
t2 := t1 − t2 = 148.8 degC Ans.
2⋅ CP

7 5
3.22 CP := ⋅R CV := ⋅R T1 := 303.15⋅ K T3 := 403.15⋅ K
2 2

P1 := 1⋅ bar P3 := 10⋅ bar

∆U := CV⋅ ( T3 − T1) ∆H := CP⋅ ( T3 − T1)

kJ kJ
∆U = 2.079 Ans. ∆H = 2.91 Ans.
mol mol

Each part consists of two steps, 12 & 23.

T2
(a) T2 := T3 P2 := P1⋅
T1

⎛ P3 ⎞
W23 := R⋅ T2⋅ ln ⎜ Work := W23
⎝ P2 ⎠
kJ
Work = 6.762 Ans.
mol

Q := ∆U − Work

kJ
Q = −4.684 Ans.
mol

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 (b) P2 := P1 T2 := T3 ∆U12 := CV⋅ ( T2 − T1)

∆H12 := CP⋅ ( T2 − T1) Q12 := ∆H12

kJ
W12 := ∆U12 − Q12 W12 = −0.831
mol

⎛ P3 ⎞ kJ
W23 := R⋅ T2⋅ ln ⎜ W23 = 7.718
⎝ P2 ⎠ mol

kJ
Work := W12 + W23 Work = 6.886 Ans.
mol

kJ
Q := ∆U − Work Q = −4.808 Ans.
mol

⎛ P2 ⎞
(c) T2 := T1 P2 := P3 W12 := R⋅ T1⋅ ln ⎜
⎝ P1 ⎠
∆H23 := CP⋅ ( T3 − T2) Q23 := ∆H23

∆U23 := CV⋅ ( T3 − T2) W23 := ∆U23 − Q23

kJ
Work := W12 + W23 Work = 4.972 Ans.
mol
kJ
Q := ∆U − Work Q = −2.894 Ans.
mol

For the second set of heat-capacity values, answers are (kJ/mol):

∆U = 1.247 ∆U = 2.079
(a) Work = 6.762 Q = −5.515
(b) Work = 6.886 Q = −5.639
(c) Work = 4.972 Q = −3.725

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 3.23 T1 := 303.15⋅ K T2 := T1 T3 := 393.15⋅ K

7 5
P1 := 1⋅ bar P3 := 12⋅ bar CP := ⋅R CV := ⋅R
2 2

For the process: ∆U := CV⋅ ( T3 − T1) ∆H := CP⋅ ( T3 − T1)

kJ kJ
∆U = 1.871 ∆H = 2.619 Ans.
mol mol

T1 ⎛ P2 ⎞
Step 12: P2 := P3⋅ W12 := R⋅ T1⋅ ln ⎜
T3 ⎝ P1 ⎠
kJ kJ
W12 = 5.608 Q12 := −W12 Q12 = −5.608
mol mol

kJ
Step 23: W23 := 0⋅ Q23 := ∆U
mol

For the process: Work := W12 + W23

kJ kJ
Q := Q12 + Q23 Work = 5.608 Q = −3.737 Ans.
mol mol

3.24 W12 = 0 Work = W23 = −P2 ( V3 − V2) = −R⋅ ( T3 − T2)

But T3 = T1 So... Work = R⋅ ( T2 − T1)

W = R⋅ T1⋅ ln ⎛⎜
P⎞
Also Therefore
⎝ P1 ⎠
T2 − T1
ln ⎛⎜
P⎞
= T2 := 350⋅ K T1 := 800⋅ K P1 := 4⋅ bar
⎝ P1 ⎠ T1

⎛ T2 − T1 ⎞
P := P1⋅ exp ⎜ P = 2.279 bar Ans.
⎝ T1 ⎠

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 3 ∆P
3.25 VA := 256⋅ cm Define: = r r := −0.0639
P1

Assume ideal gas; let V represent total volume:

P1⋅ VB = P2⋅ ( VA + VB) From this one finds:

∆P −V A −VA⋅ ( r + 1) 3
= VB := VB = 3750.3 cm Ans.
P1 VA + VB r

7 CP
3.26 T1 := 300⋅ K P1 := 1⋅ atm CP := ⋅R CV := CP − R γ :=
2 CV

The process occurring in section B is a reversible, adiabatic compression. Let

P ( final) = P2 TA ( final) = TA TB ( final) = TB

nA = nB Since the total volume is constant,

2⋅ nA⋅ R⋅ T1 nA⋅ R⋅ ( TA + TB) 2⋅ T1 TA + TB

= or = (1)
P1 P2 P1 P2

γ −1
γ
⎛ P2 ⎞
(a) P2 := 1.25⋅ atm TB := T1⋅ ⎜ (2)
⎝ P1 ⎠

( )
P2
TA := 2⋅ T1⋅ − TB Q = nA⋅ ∆UA + ∆UB
P1

q := CV⋅ ( TA + TB − 2⋅ T1)
Q
Define q= (3)
nA
kJ
TB = 319.75 K TA = 430.25 K q = 3.118 Ans.
mol

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 (b) Combine Eqs. (1) & (2) to eliminate the ratio of pressures:

TA := 425⋅ K (guess) TB := 300⋅ K

γ −1
γ
⎛ TA + TB ⎞
Given TB = T1⋅ ⎜ TB := Find ( TB)
⎝ 2⋅ T1 ⎠
TB = 319.02 K Ans.

⎛ TA + TB ⎞
P2 := P1⋅ ⎜ (1) P2 = 1.24 atm Ans.
⎝ 2⋅ T1 ⎠
q := CV⋅ ( TA + TB − 2⋅ T1)
kJ
q = 2.993 Ans.
mol

(c) TB := 325⋅ K By Eq. (2),

γ
γ −1
⎛ TB ⎞
P2 := P1⋅ ⎜ P2 = 1.323 atm Ans.
⎝ T1 ⎠

P2
TA := 2⋅ T1⋅ − TB (1) TA = 469 K Ans.
P1

q := CV⋅ ( TA + TB − 2⋅ T1)
kJ
q = 4.032 Ans.
mol

(d) Eliminate TA + TB from Eqs. (1) & (3):

kJ q⋅ P1
q := 3⋅ P2 := + P1 P2 = 1.241 atm Ans.
mol 2⋅ T1⋅ CV
γ −1
γ
⎛ P2 ⎞
TB := T1⋅ ⎜ (2) TB = 319.06 K Ans.
⎝ P1 ⎠
P2
TA := 2⋅ T1⋅ − TB (1) TA = 425.28 K Ans.
P1

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 3 6
cm cm
3.30 B := −242.5⋅ C := 25200⋅ T := 373.15⋅ K
mol 2
mol
P1 := 1⋅ bar P2 := 55⋅ bar
B
B' := −3 1
R⋅ T B' = −7.817 × 10
bar
2
C−B
C' := −5 1
2 2 C' = −3.492 × 10
R ⋅T 2
bar
(a) Solve virial eqn. for initial V.
R⋅ T
Guess: V1 :=
P1
P 1⋅ V 1 3
V1 := Find ( V1)
B C cm
Given = 1+ + V1 = 30780
R⋅ T V1 V 2 mol
1
Solve virial eqn. for final V.
R⋅ T
Guess: V2 :=
P2

P 2⋅ V 2 3
V2 := Find ( V2)
B C cm
Given = 1+
+ V2 = 241.33
R⋅ T V2 V 2 mol
2
Eliminate P from Eq. (1.3) by the virial equation:
V2
⌠ ⎛ B C⎞ 1
Work := −R⋅ T⋅ ⎮ ⎜ 1 + + ⋅ dV kJ
Work = 12.62 Ans.
⎮ ⎝ V V2 V
⎠ mol
⌡V
1
(b) Eliminate dV from Eq. (1.3) by the virial equation in P:
P
⎛ −1 ⎞ ⌠ 2 ⎛ −1 + C'⋅ P⎞ dP
dV = R⋅ T⋅ ⎜ + C' ⋅ dP W := −R⋅ T⋅ ⎮ ⎜
⎝P
2
⎠
⎮
⌡P ⎝P ⎠
1

kJ
W = 12.596 Ans.
mol

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 Note: The answers to (a) & (b) differ because the relations between the two
sets of parameters are exact only for infinite series.

T
3.32 Tc := 282.3⋅ K T := 298.15⋅ K Tr := Tr = 1.056
Tc

P
Pc := 50.4⋅ bar P := 12⋅ bar Pr := Pr = 0.238
Pc
ω := 0.087 (guess)
3 6 3
cm cm R⋅ T cm
(a) B := −140⋅ C := 7200⋅ V := V = 2066
mol 2 P mol
mol
Given P⋅ V B C
= 1+ +
R⋅ T V V2
3
cm P⋅ V
V := Find ( V) V = 1919 Z := Z = 0.929 Ans.
mol R⋅ T

0.422
(b) B0 := 0.083 − B0 = −0.304
1.6
Tr

0.172 −3
B1 := 0.139 − B1 = 2.262 × 10
4.2
Tr
3
Pr Z⋅ R ⋅ T
(
Z := 1 + B0 + ω ⋅ B1 ⋅ ) Tr
Z = 0.932 V :=
P
V = 1924
cm
mol
Ans.

(c) For Redlich/Kwong EOS:

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748 Table 3.1

Ψ ⋅ α ( Tr )
q ( Tr) :=
− 0.5
α ( Tr) := Tr Table 3.1 Eq. (3.54)
Ω ⋅ Tr
Ω ⋅ Pr
β ( Tr , Pr) := Eq. (3.53)
Tr

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 Calculate Z Guess: Z := 0.9

Given Eq. (3.52)

Z − β ( T r , Pr )
Z = 1 + β ( T r , Pr ) − q ( T r ) ⋅ β ( T r , Pr ) ⋅
( Z + ε ⋅ β ( T r , Pr ) ) ⋅ ( Z + σ ⋅ β ( T r , Pr ) )
3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.928 V := V = 1916.5 Ans.
P mol

(d) For SRK EOS:

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748 Table 3.1

2
⎡ ⎛ 1⎞ ⎤

α ( Tr , ω ) := ⎣ 1 + ( 0.480 + 1.574ω − 0.176ω ) ⋅ ⎝ 1 − Tr ⎠ ⎦

⎢ 2 ⎜ 2 ⎥
Table 3.1

q ( Tr) :=
(
Ψ ⋅ α Tr , ω ) Eq. (3.54) β ( Tr , Pr) :=
Ω ⋅ Pr
Eq. (3.53)
Ω ⋅ Tr Tr

Calculate Z Guess: Z := 0.9

Given Eq. (3.52)

Z − β ( T r , Pr )
Z = 1 + β ( T r , Pr ) − q ( T r ) ⋅ β ( T r , Pr ) ⋅
( Z + ε ⋅ β ( T r , Pr ) ) ⋅ ( Z + σ ⋅ β ( T r , Pr ) )
3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.928 V := V = 1918 Ans.
P mol

(e) For Peng/Robinson EOS:

σ := 1 + 2 ε := 1 − 2 Ω := 0.07779 Ψ := 0.45724 Table 3.1

2
⎡ ⎛ 1⎞ ⎤

α ( Tr , ω ) := ⎣ 1 + ( 0.37464 + 1.54226ω − 0.26992ω ) ⋅ ⎝ 1 − Tr ⎠ ⎦

⎢ 2 ⎜ 2 ⎥ Table 3.1

q ( Tr) :=
(
Ψ ⋅ α Tr , ω ) Eq. (3.54) β ( Tr , Pr) :=
Ω ⋅ Pr
Eq. (3.53)
Ω ⋅ Tr Tr

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 Calculate Z Guess: Z := 0.9

Given Eq. (3.52)

Z − β ( T r , Pr )
Z = 1 + β ( T r , Pr ) − q ( T r ) ⋅ β ( T r , Pr ) ⋅
( Z + ε ⋅ β ( T r , Pr ) ) ⋅ ( Z + σ ⋅ β ( T r , Pr ) )
3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.92 V := V = 1900.6 Ans.
P mol

T
3.33 Tc := 305.3⋅ K T := 323.15⋅ K Tr := Tr = 1.058
Tc

P
Pc := 48.72⋅ bar P := 15⋅ bar Pr := Pr = 0.308
Pc
ω := 0.100 (guess)
3 6 3
cm cm R⋅ T cm
(a) B := −156.7⋅ C := 9650⋅ V := V = 1791
mol 2 P mol
mol

Given P⋅ V B C
= 1+ +
R⋅ T V V2

3
cm P⋅ V
V := Find ( V) V = 1625 Z := Z = 0.907 Ans.
mol R⋅ T

0.422
(b) B0 := 0.083 − B0 = −0.302
1.6
Tr

0.172 −3
B1 := 0.139 − B1 = 3.517 × 10
4.2
Tr

3
Pr Z⋅ R ⋅ T
(
Z := 1 + B0 + ω ⋅ B1 ⋅ ) Tr
Z = 0.912 V :=
P
V = 1634
cm
mol
Ans.

(c) For Redlich/Kwong EOS:

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748 Table 3.1

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 Ψ ⋅ α ( Tr )
q ( Tr) :=
− 0.5
α ( Tr) := Tr Table 3.1 Eq. (3.54)
Ω ⋅ Tr
Ω ⋅ Pr
β ( Tr , Pr) := Eq. (3.53)
Tr

Calculate Z Guess: Z := 0.9

Given Eq. (3.52)

Z − β ( T r , Pr )
Z = 1 + β ( T r , Pr ) − q ( T r ) ⋅ β ( T r , Pr ) ⋅
( Z + ε ⋅ β ( T r , Pr ) ) ⋅ ( Z + σ ⋅ β ( T r , Pr ) )
3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.906 V := V = 1622.7 Ans.
P mol

(d) For SRK EOS:

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748 Table 3.1

2
⎡ ⎛ 1⎞ ⎤

α ( Tr , ω ) := ⎣ 1 + 0.480 + 1.574ω − 0.176ω ) ⋅ ⎝ 1 − Tr ⎠ ⎦

⎢ ( 2 ⎜ 2 ⎥
Table 3.1

q ( Tr) :=
(
Ψ ⋅ α Tr , ω ) Eq. (3.54) β ( Tr , Pr) :=
Ω ⋅ Pr
Eq. (3.53)
Ω ⋅ Tr Tr

Calculate Z Guess: Z := 0.9

Given Eq. (3.52)

Z − β ( T r , Pr )
Z = 1 + β ( T r , Pr ) − q ( T r ) ⋅ β ( T r , Pr ) ⋅
( Z + ε ⋅ β ( T r , Pr ) ) ⋅ ( Z + σ ⋅ β ( T r , Pr ) )
3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.907 V := V = 1624.8 Ans.
P mol

(e) For Peng/Robinson EOS:

σ := 1 + 2 ε := 1 − 2 Ω := 0.07779 Ψ := 0.45724 Table 3.1

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 2
⎡ ⎛ 1⎞ ⎤

α ( Tr , ω ) := ⎣ 1 + ( 0.37464 + 1.54226ω − 0.26992ω ) ⋅ ⎝ 1 − Tr ⎠ ⎦

⎢ 2 ⎜ 2 ⎥ Table 3.1

q ( Tr) :=
(
Ψ ⋅ α Tr , ω ) Eq. (3.54) β ( Tr , Pr) :=
Ω ⋅ Pr
Eq. (3.53)
Ω ⋅ Tr Tr

Calculate Z Guess: Z := 0.9

Given Eq. (3.52)

Z − β ( T r , Pr )
Z = 1 + β ( T r , Pr ) − q ( T r ) ⋅ β ( T r , Pr ) ⋅
( Z + ε ⋅ β ( T r , Pr ) ) ⋅ ( Z + σ ⋅ β ( T r , Pr ) )
3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.896 V := V = 1605.5 Ans.
P mol

T
3.34 Tc := 318.7⋅ K T := 348.15⋅ K Tr := Tr = 1.092
Tc

P
Pc := 37.6⋅ bar P := 15⋅ bar Pr := Pr = 0.399
Pc

ω := 0.286
(guess)
3 6 3
cm cm R⋅ T cm
(a) B := −194⋅ C := 15300⋅ V := V = 1930
mol 2 P mol
mol

Given P⋅ V B C
= 1+ +
R⋅ T V V2

3
cm P⋅ V
V := Find ( V) V = 1722 Z := Z = 0.893 Ans.
mol R⋅ T
0.422
(b) B0 := 0.083 − B0 = −0.283
1.6
Tr

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 0.172
B1 := 0.139 − B1 = 0.02
4.2
Tr
3
Pr Z⋅ R ⋅ T
(
Z := 1 + B0 + ω ⋅ B1 ⋅ ) Tr
Z = 0.899 V :=
P
V = 1734
cm
mol
Ans.

(c) For Redlich/Kwong EOS:

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748 Table 3.1

Ψ ⋅ α ( Tr )
q ( Tr) :=
− 0.5
α ( Tr) := Tr Table 3.1 Eq. (3.54)
Ω ⋅ Tr
Ω ⋅ Pr
β ( Tr , Pr) := Eq. (3.53)
Tr

Calculate Z Guess: Z := 0.9

Given Eq. (3.52)

Z − β ( T r , Pr )
Z = 1 + β ( T r , Pr ) − q ( T r ) ⋅ β ( T r , Pr ) ⋅
( Z + ε ⋅ β ( T r , Pr ) ) ⋅ ( Z + σ ⋅ β ( T r , Pr ) )
3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.888 V := V = 1714.1 Ans.
P mol

(d) For SRK EOS:

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748 Table 3.1

2
⎡ ⎛ 1⎞ ⎤

α ( Tr , ω ) := ⎣ 1 + 0.480 + 1.574ω − 0.176ω ) ⋅ ⎝ 1 − Tr ⎠ ⎦

⎢ ( 2 ⎜ 2 ⎥
Table 3.1

q ( Tr) :=
(
Ψ ⋅ α Tr , ω ) Eq. (3.54) β ( Tr , Pr) :=
Ω ⋅ Pr
Eq. (3.53)
Ω ⋅ Tr Tr

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 Calculate Z Guess: Z := 0.9
Given Eq. (3.52)

Z − β ( T r , Pr )
Z = 1 + β ( T r , Pr ) − q ( T r ) ⋅ β ( T r , Pr ) ⋅
( Z + ε ⋅ β ( T r , Pr ) ) ⋅ ( Z + σ ⋅ β ( T r , Pr ) )
3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.895 V := V = 1726.9 Ans.
P mol
(e) For Peng/Robinson EOS:

σ := 1 + 2 ε := 1 − 2 Ω := 0.07779 Ψ := 0.45724 Table 3.1

2
⎡ ⎛ 1⎞ ⎤

α ( Tr , ω ) := ⎣ 1 + ( 0.37464 + 1.54226ω − 0.26992ω ) ⋅ ⎝ 1 − Tr ⎠ ⎦

⎢ 2 ⎜ 2 ⎥ Table 3.1

q ( Tr) :=
(
Ψ ⋅ α Tr , ω ) Eq. (3.54) β ( Tr , Pr) :=
Ω ⋅ Pr
Eq. (3.53)
Ω ⋅ Tr Tr

Calculate Z Guess: Z := 0.9

Given Eq. (3.52)

Z − β ( T r , Pr )
Z = 1 + β ( T r , Pr ) − q ( T r ) ⋅ β ( T r , Pr ) ⋅
( Z + ε ⋅ β ( T r , Pr ) ) ⋅ ( Z + σ ⋅ β ( T r , Pr ) )
3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.882 V := V = 1701.5 Ans.
P mol

3.35 T := 523.15⋅ K P := 1800⋅ kPa

3 6
cm cm R⋅ T
(a) B := −152.5⋅ C := −5800⋅ V := (guess)
mol 2 P
mol

P⋅ V B C
Given = 1+ + V := Find ( V)
R⋅ T V V2
3
P⋅ V cm
Z := V = 2250 Z = 0.931 Ans.
R⋅ T mol

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 (b) Tc := 647.1⋅ K Pc := 220.55⋅ bar ω := 0.345

T P 0.422
Tr := Pr := B0 := 0.083 −
Tc Pc 1.6
Tr
Tr = 0.808 Pr = 0.082 B0 = −0.51

Pr
B1 := 0.139 −
0.172
4.2
B1 = −0.281 (
Z := 1 + B0 + ω ⋅ B1 ⋅ ) Tr
Tr

3
Z⋅ R ⋅ T cm
V := Z = 0.939 V = 2268 Ans.
P mol
3
gm cm
(c) Table F.2: molwt := 18.015⋅ V := 124.99⋅ ⋅ molwt
mol gm
3
cm
or V = 2252 Ans.
mol

3 6 9
cm cm cm
3.37 B := −53.4⋅ C := 2620⋅ D := 5000⋅ n := mol
mol 2 3
mol mol
T := 273.15⋅ K

P⋅ V B C D
Given = 1+ + + f ( P , V) := Find ( V)
R⋅ T V V2 V3

i := 0 .. 10 Pi := 10 ( − 10 )
+ 20⋅ i ⋅ bar Vi :=
R⋅ T
(guess)
Pi
f ( P i , V i ) ⋅ Pi
Zi := Eq. (3.12)
R⋅ T
B ⋅ Pi 1 1 B ⋅ Pi Eq. (3.39)
Z1i := 1 + Eq. (3.38) Z2i := + +
R⋅ T 2 4 R⋅ T

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 1·10 -10 Zi = Z1i = Z2i =
20 1 1 1
40 0.953 0.953 0.951
60 0.906 0.906 0.895
80 0.861 0.859 0.83
Pi = 100 bar 0.819 0.812 0.749
120 0.784 0.765 0.622
140 0.757 0.718 0.5+0.179i
160 0.74 0.671 0.5+0.281i
180 0.733 0.624 0.5+0.355i
200 0.735 0.577 0.5+0.416i
0.743 0.53 0.5+0.469i

Note that values of Z from Eq. (3.39) are not physically meaningful for
pressures above 100 bar.

0.9

Zi
0.8
Z1 i

Z2 i 0.7

0.6

0.5
0 50 100 150 200
−1
Pi⋅ bar

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 3.38 (a) Propane: Tc := 369.8⋅ K Pc := 42.48⋅ bar ω := 0.152

T := 313.15⋅ K P := 13.71⋅ bar

T P
Tr := Tr = 0.847 Pr := Pr = 0.323
Tc Pc

For Redlich/Kwong EOS:

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748 Table 3.1

Ψ ⋅ α ( Tr )
q ( Tr) :=
− 0.5
α ( Tr) := Tr Table 3.1 Eq. (3.54)
Ω ⋅ Tr
Ω ⋅ Pr
β ( Tr , Pr) := Eq. (3.53)
Tr

Calculate Z for liquid by Eq. (3.56) Guess: Z := 0.01

Given
⎛ 1 + β ( T r , Pr ) − Z ⎞
( )(
Z = β ( T r , Pr ) + Z + ε ⋅ β ( T r , Pr ) ⋅ Z + σ ⋅ β ( T r , Pr ) ⋅ ⎜ )
⎝ q ( T r ) ⋅ β ( T r , Pr ) ⎠
3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.057 V := V = 108.1 Ans.
P mol

Calculate Z for vapor by Eq. (3.52) Guess: Z := 0.9

Given
Z − β ( T r , Pr )
Z = 1 + β ( T r , Pr ) − q ( T r ) ⋅ β ( T r , Pr ) ⋅
(
Z ⋅ Z + β ( T r , Pr ) )
3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.789 V := V = 1499.2 Ans.
P mol

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 T
Rackett equation for saturated liquid: Tr := Tr = 0.847
Tc
3
cm
Vc := 200.0⋅ Zc := 0.276
mol

⎡( 1−Tr) 0.2857⎤ 3
V := Vc⋅ Zc⎣ ⎦ cm
V = 94.17 Ans.
mol

For saturated vapor, use Pitzer correlation:

0.422
B0 := 0.083 −
1.6 B0 = −0.468
Tr

0.172
B1 := 0.139 −
4.2 B1 = −0.207
Tr

3
R⋅ T Tc
V :=
P
(
+ R⋅ B0 + ω ⋅ B1 ⋅ )
Pc
V = 1.538 × 10
3 cm
mol
Ans.

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 Parts (b) through (t) are worked exactly the same way. All results are
summarized as follows. Volume units are cu.cm./mole.
R/K, Liq. R/K, Vap. Rackett Pitzer
(a) 108.1 1499.2 94.2 1537.8

(b) 114.5 1174.7 98.1 1228.7

(c) 122.7 920.3 102.8 990.4

(d) 133.6 717.0 109.0 805.0

(e) 148.9 1516.2 125.4 1577.0

(f) 158.3 1216.1 130.7 1296.8

(g) 170.4 971.1 137.4 1074.0

(h) 187.1 768.8 146.4 896.0

(i) 153.2 1330.3 133.9 1405.7

(j) 164.2 1057.9 140.3 1154.3

(k) 179.1 835.3 148.6 955.4

(l) 201.4 645.8 160.6 795.8

(m) 61.7 1252.5 53.5 1276.9

(n) 64.1 1006.9 55.1 1038.5

(o) 66.9 814.5 57.0 853.4

(p) 70.3 661.2 59.1 707.8

(q) 64.4 1318.7 54.6 1319.0

(r) 67.4 1046.6 56.3 1057.2

(s) 70.8 835.6 58.3 856.4

(t) 74.8 669.5 60.6 700.5

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 3.39 (a) Propane Tc := 369.8⋅ K Pc := 42.48⋅ bar ω := 0.152

T := ( 40 + 273.15) ⋅ K T = 313.15 K P := 13.71⋅ bar

T P
Tr := Tr = 0.847 Pr := Pr = 0.323
Tc Pc

From Table 3.1 for SRK:

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748

2
⎡ ⎛ 1⎞ ⎤

α ( Tr , ω ) := ⎣ 1 + 0.480 + 1.574ω − 0.176ω ) ⋅ ⎝ 1 − Tr ⎠ ⎦

⎢ ( 2 ⎜ 2 ⎥

q ( Tr) :=
(
Ψ ⋅ α Tr , ω ) Eq. (3.54) β ( Tr , Pr) :=
Ω ⋅ Pr
Eq. (3.53)
Ω ⋅ Tr Tr

Calculate Z for liquid by Eq. (3.56) Guess: Z := 0.01

Given
⎛ 1 + β ( T r , Pr ) − Z ⎞
( )(
Z = β ( T r , Pr ) + Z + ε ⋅ β ( T r , Pr ) ⋅ Z + σ ⋅ β ( T r , Pr ) ⋅ ⎜ )
⎝ q ( T r ) ⋅ β ( T r , Pr ) ⎠
3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.055 V := V = 104.7 Ans.
P mol

Calculate Z for vapor by Eq. (3.52) Guess: Z := 0.9

Given
Z − β ( T r , Pr )
Z = 1 + β ( T r , Pr ) − q ( T r ) ⋅ β ( T r , Pr ) ⋅
( Z + ε ⋅ β ( T r , Pr ) ) ⋅ ( Z + σ ⋅ β ( T r , Pr ) )

3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.78 V := V = 1480.7 Ans.
P mol

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 Parts (b) through (t) are worked exactly the same way. All results are
summarized as follows. Volume units are cu.cm./mole.
SRK, Liq. SRK, Vap. Rackett Pitzer
(a) 104.7 1480.7 94.2 1537.8

(b) 110.6 1157.8 98.1 1228.7

(c) 118.2 904.9 102.8 990.4

(d) 128.5 703.3 109.0 805.0

(e) 142.1 1487.1 125.4 1577.0

(f) 150.7 1189.9 130.7 1296.8

(g) 161.8 947.8 137.4 1074.0

(h) 177.1 747.8 146.4 896.0

(i) 146.7 1305.3 133.9 1405.7

(j) 156.9 1035.2 140.3 1154.3

(k) 170.7 815.1 148.6 955.4

(l) 191.3 628.5 160.6 795.8

(m) 61.2 1248.9 53.5 1276.9

(n) 63.5 1003.2 55.1 1038.5

(o) 66.3 810.7 57.0 853.4

(p) 69.5 657.4 59.1 707.8

(q) 61.4 1296.8 54.6 1319.0

(r) 63.9 1026.3 56.3 1057.2

(s) 66.9 817.0 58.3 856.4

(t) 70.5 652.5 60.6 700.5

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 3.40 (a) Propane Tc := 369.8⋅ K Pc := 42.48⋅ bar ω := 0.152

T := ( 40 + 273.15) ⋅ K T = 313.15 K P := 13.71⋅ bar

T P
Tr := Tr = 0.847 Pr := Pr = 0.323
Tc Pc

From Table 3.1 for PR:

2
⎡ ⎛ 1⎞ ⎤

α ( Tr , ω ) := ⎣ 1 + 0.37464 + 1.54226ω − 0.26992ω ) ⋅ ⎝ 1 − Tr ⎠ ⎦

⎢ ( 2 ⎜ 2 ⎥

σ := 1 + 2 ε := 1 − 2 Ω := 0.07779 Ψ := 0.45724

q ( Tr) :=
(
Ψ ⋅ α Tr , ω ) Eq. (3.54) β ( Tr , Pr) :=
Ω ⋅ Pr
Eq. (3.53)
Ω ⋅ Tr Tr

Calculate Z for liquid by Eq. (3.56) Guess: Z := 0.01

Given
⎛ 1 + β ( T r , Pr ) − Z ⎞
( )(
Z = β ( T r , Pr ) + Z + ε ⋅ β ( T r , Pr ) ⋅ Z + σ ⋅ β ( T r , Pr ) ⋅ ⎜ )
⎝ q ( T r ) ⋅ β ( T r , Pr ) ⎠

3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.049 V := V = 92.2 Ans.
P mol

Calculate Z for vapor by Eq. (3.52) Guess: Z := 0.6

Given
Z − β ( T r , Pr )
Z = 1 + β ( T r , Pr ) − q ( T r ) ⋅ β ( T r , Pr ) ⋅
( Z + ε ⋅ β ( T r , Pr ) ) ⋅ ( Z + σ ⋅ β ( T r , Pr ) )
3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 0.766 V := V = 1454.5 Ans.
P mol

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 Parts (b) through (t) are worked exactly the same way. All results are
summarized as follows. Volume units are cu.cm./mole.
PR, Liq. PR, Vap. Rackett Pitzer
(a) 92.2 1454.5 94.2 1537.8

(b) 97.6 1131.8 98.1 1228.7

(c) 104.4 879.2 102.8 990.4

(d) 113.7 678.1 109.0 805.0

(e) 125.2 1453.5 125.4 1577.0

(f) 132.9 1156.3 130.7 1296.8

(g) 143.0 915.0 137.4 1074.0

(h) 157.1 715.8 146.4 896.0

(i) 129.4 1271.9 133.9 1405.7

(j) 138.6 1002.3 140.3 1154.3

(k) 151.2 782.8 148.6 955.4

(l) 170.2 597.3 160.6 795.8

(m) 54.0 1233.0 53.5 1276.9

(n) 56.0 987.3 55.1 1038.5

(o) 58.4 794.8 57.0 853.4

(p) 61.4 641.6 59.1 707.8

(q) 54.1 1280.2 54.6 1319.0

(r) 56.3 1009.7 56.3 1057.2

(s) 58.9 800.5 58.3 856.4

(t) 62.2 636.1 60.6 700.5

51

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 gm
3.41 (a) For ethylene, molwt := 28.054 Tc := 282.3⋅ K Pc := 50.40⋅ bar
mol
ω := 0.087 T := 328.15⋅ K P := 35⋅ bar
T P
Tr := Pr := Tr = 1.162 Pr = 0.694
Tc Pc

From Tables E.1 & E.2: Z0 := 0.838 Z1 := 0.033

Z := Z0 + ω ⋅ Z1 Z = 0.841

18⋅ kg Z⋅ n⋅ R⋅ T 3
n := Vtotal := Vtotal = 0.421 m Ans.
molwt P

3
(b) T := 323.15⋅ K P := 115⋅ bar Vtotal := 0.25⋅ m

T P
Tr := Tr = 1.145 Pr := Pr = 2.282
Tc Pc

From Tables E.3 & E.4: Z0 := 0.482 Z1 := 0.126

P⋅ Vtotal
Z := Z0 + ω ⋅ Z1 Z = 0.493 n := n = 2171 mol
Z⋅ R⋅ T
mass := n⋅ molwt mass = 60.898 kg Ans.

3.42 Assume validity of Eq. (3.38).

3
cm
P1 := 1bar T1 := 300K V1 := 23000
mol
P1⋅ V1 R ⋅ T1 3
⋅ ( Z1 − 1)
3 cm
Z1 := Z1 = 0.922 B := B = −1.942 × 10
R⋅ T1 P1 mol

With this B, recalculate at P2 P2 := 5bar

B ⋅ P2 R ⋅ T 1⋅ Z 2 3 cm
3
Z2 := 1 + Z2 = 0.611 V2 := V2 = 3.046 × 10 Ans.
R⋅ T1 P2 mol

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 T
3.43 T := 753.15⋅ K Tc := 513.9⋅ K Tr := Tr = 1.466
Tc

P := 6000⋅ kPa Pc := 61.48⋅ bar P

Pr := Pr = 0.976
Pc
ω := 0.645 0.422
B0 := 0.083 − B0 = −0.146
1.6
Tr
0.172
B1 := 0.139 − B1 = 0.104
4.2
Tr

3
R⋅ T Tc
V :=
P
(
+ B0 + ω ⋅ B1 ⋅ R⋅ )
Pc
V = 989
cm
mol
Ans.

3
R⋅ T cm
For an ideal gas: V := V = 1044
P mol

3.44 T := 320⋅ K P := 16⋅ bar Tc := 369.8⋅ K Pc := 42.48⋅ bar

3
cm
ω := 0.152 Vc := 200⋅ Zc := 0.276 gm
mol molwt := 44.097
mol
T P
Tr := Tr = 0.865 Pr := Pr = 0.377
Tc Pc

⎡( 1−Tr) 0.2857⎤ 3
Vliq := Vc⋅ Zc⎣ ⎦ cm
Vliq = 96.769
mol

3 0.8⋅ Vtank
Vtank := 0.35⋅ m mliq := mliq = 127.594 kg Ans.
Vliq
molwt
0.422
B0 := 0.083 − B0 = −0.449
1.6
Tr

0.172
B1 := 0.139 − B1 = −0.177
4.2
Tr

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 3
R⋅ T Tc
Vvap :=
P
(
+ B0 + ω ⋅ B1 ⋅ R⋅
Pc
) Vvap = 1.318 × 10
3 cm
mol

0.2⋅ Vtank
mvap :=
Vvap mvap = 2.341 kg Ans.
molwt

T
3.45 T := 298.15⋅ K Tc := 425.1⋅ K Tr := Tr = 0.701
Tc
P
P := 2.43⋅ bar Pc := 37.96⋅ bar Pr := Pr = 0.064
Pc

3 gm
ω := 0.200 Vvap := 16⋅ m molwt := 58.123⋅
mol

0.422
B0 := 0.083 − B0 = −0.661
1.6
Tr

0.172
B1 := 0.139 − B1 = −0.624
4.2
Tr

3
R⋅ T Tc
V :=
P
(
+ B0 + ω ⋅ B1 ⋅ R⋅ )
Pc
V = 9.469 × 10
3 cm
mol
Vvap
mvap := mvap = 98.213 kg Ans.
V
molwt

T
3.46 (a) T := 333.15⋅ K Tc := 305.3⋅ K Tr := Tr = 1.091
Tc

P
P := 14000⋅ kPa Pc := 48.72⋅ bar Pr := Pr = 2.874
Pc

3 gm
ω := 0.100 Vtotal := 0.15⋅ m molwt := 30.07
mol

From tables E.3 & E.4: Z0 := 0.463 Z1 := −0.037

54

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 3
Z⋅ R ⋅ T cm
Z := Z0 + ω ⋅ Z1 Z = 0.459 V := V = 90.87
P mol
Vtotal
methane := methane = 49.64 kg Ans.
V
molwt

(b) Vtotal
V := P := 20000⋅ kPa P⋅ V = Z ⋅ R ⋅ T = Z ⋅ R ⋅ T r ⋅ T c
40⋅ kg

α P⋅ V mol
or Tr = where α := α = 29.548
Z R ⋅ Tc kg

0.889 P
Whence Tr = at Pr := Pr = 4.105
Z Pc

This equation giving Tr as a function of Z and Eq. (3.57) in conjunction with

Tables E.3 & E.4 are two relations in the same variables which must be
satisfied at the given reduced pressure. The intersection of these two
relations can be found by one means or another to occur at about:
Tr := 1.283 and Z := 0.693

Whence T := Tr⋅ Tc

T = 391.7 K or 118.5⋅ degC Ans.

3.47 Vtotal := 0.15⋅ m3 T := 298.15⋅ K

gm
Tc := 282.3⋅ K Pc := 50.40⋅ bar ω := 0.087 molwt := 28.054
mol
Vtotal
V := P⋅ V = Pr⋅ Pc⋅ V = Z⋅ R⋅ T
⎛ 40⋅ kg ⎞
⎜
⎝ molwt ⎠
R⋅ T
or Pr = α ⋅ Z where α := α = 4.675
Pc⋅ V
T
Whence Pr = 4.675⋅ Z at Tr := Tr = 1.056
Tc

55

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 This equation giving Pr as a function of Z and Eq. (3.57) in conjunction with
Tables E.3 & E.4 are two relations in the same variables which must be
satisfied at the given reduced temperature. The intersection of these two
relations can be found by one means or another to occur at about:

Pr := 1.582 and Z := 0.338 P := Pc⋅ Pr P = 79.73 bar Ans.

Vtotal 3
3 cm
3.48 mwater := 15⋅ kg Vtotal := 0.4⋅ m V := V = 26.667
mwater gm

Interpolate in Table F.2 at 400 degC to find: P = 9920⋅ kPa Ans.

T1
3.49 T1 := 298.15⋅ K Tc := 305.3⋅ K Tr1 := Tr1 = 0.977
Tc
P1
P1 := 2200⋅ kPa Pc := 48.72⋅ bar Pr1 := Pr1 = 0.452
Pc
3
Vtotal := 0.35⋅ m ω := 0.100
From Tables E.1 & E.2: Z0 := .8105 Z1 := −0.0479

Z⋅ R⋅ T1 cm
3
Z := Z0 + ω ⋅ Z1 Z = 0.806 V1 := V1 = 908
P1 mol
T2
T2 := 493.15⋅ K Tr2 := Tr2 = 1.615
Tc
Assume Eq. (3.38) applies at the final state.
0.422
B0 := 0.083 − B0 = −0.113
1.6
Tr2

0.172
B1 := 0.139 − B1 = 0.116
4.2
Tr2

R⋅ T2
P2 :=
Tc P2 = 42.68 bar Ans.
(
V1 − B0 + ω ⋅ B1 ⋅ R⋅ ) Pc

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 T
3.50 T := 303.15⋅ K Tc := 304.2⋅ K Tr := Tr = 0.997
Tc
3 gm
Vtotal := 0.5⋅ m Pc := 73.83⋅ bar ω := 0.224 molwt := 44.01⋅
mol
0.422
B0 := 0.083 − B0 = −0.341
1.6
Tr

0.172
B1 := 0.139 − B1 = −0.036
4.2
Tr
Vtotal 3
V := 3 cm
V = 2.2 × 10
⎛ 10⋅ kg ⎞
⎜ mol
⎝ molwt ⎠
R⋅ T
P :=
Tc P = 10.863 bar Ans.
(
V − B0 + ω ⋅ B1 ⋅ R⋅ ) Pc

3.51 Basis: 1 mole of LIQUID nitrogen

Tn
Tn := 77.3⋅ K Tc := 126.2⋅ K Tr := Tr = 0.613
Tc

P
P := 1⋅ atm Pc := 34.0⋅ bar Pr := Pr = 0.03
Pc
gm
ω := 0.038 molwt := 28.014⋅ 3
mol Vliq := 34.7⋅ cm

0.422
B0 := 0.083 −
1.6 B0 = −0.842
Tr

0.172
B1 := 0.139 − B1 = −1.209
4.2
Tr
Pr
(
Z := 1 + B0 + ω ⋅ B1 ⋅ ) Tr
Z = 0.957

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 P⋅ Vliq −3
nvapor := nvapor = 5.718 × 10 mol
Z⋅ R ⋅ Tn

Final conditions:
2⋅ Vliq cm
3
ntotal := 1⋅ mol + nvapor V := V = 69.005
ntotal mol

T
T := 298.15⋅ K Tr := Tr = 2.363
Tc

R⋅ T
Pig := Pig = 359.2 bar
V

Use Redlich/Kwong at so high a P.

α ( Tr) = 0.651
− .5
Ω := 0.08664 Ψ := 0.42748 α ( Tr) := Tr

Ψ ⋅ α ( Tr ) ⋅ R ⋅ Tc
2 2
Ω ⋅ R⋅ Tc
a := Eq. (3.42) b := Eq. (3.43)
Pc Pc
3
3 bar⋅ cm 3
a = 0.901 m cm
2 b = 26.737
mol mol

R⋅ T a
P := − Eq. (3.44) P = 450.1 bar Ans.
V − b V ⋅ ( V + b)

3
cm
3.52 For isobutane: Tc := 408.1⋅ K Pc := 36.48⋅ bar V1 := 1.824⋅
gm

T1 := 300⋅ K P1 := 4⋅ bar T2 := 415⋅ K P2 := 75⋅ bar

T1 P1 T2 P2
Tr1 := Pr1 := Tr2 := Pr2 :=
Tc Pc Tc Pc

Tr1 = 0.735 Pr1 = 0.11 Tr2 = 1.017 Pr2 = 2.056

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 From Fig. (3.17): ρ r1 := 2.45
The final T > Tc, and Fig. 3.16 probably should not be used. One can easily
show that

P ⋅ Vc with Z from Eq. (3.57) and

ρr =
Z ⋅ R⋅ T Tables E.3 and E.4. Thus

3
cm
Vc := 262.7⋅ ω := 0.181 Z0 := 0.3356 Z1 := −0.0756
mol
P 2⋅ V c
Z := Z0 + ω ⋅ Z1 Z = 0.322 ρ r2 := ρ r2 = 1.774
Z⋅ R ⋅ T2

ρ r1 cm
3
Eq. (3.75): V2 := V1⋅ V2 = 2.519 Ans.
ρ r2 gm

gm
3.53 For n-pentane: Tc := 469.7⋅ K Pc := 33.7⋅ bar ρ 1 := 0.63⋅
3
cm
T1 := 291.15⋅ K P1 := 1⋅ bar T2 := 413.15⋅ K P2 := 120⋅ bar

T1 P1 T2 P2
Tr1 := Pr1 := Tr2 := Pr2 :=
Tc Pc Tc Pc

Tr1 = 0.62 Pr1 = 0.03 Tr2 = 0.88 Pr2 = 3.561

From Fig. (3.16): ρ r1 := 2.69 ρ r2 := 2.27

ρ r2 gm
By Eq. (3.75), ρ 2 := ρ 1⋅ ρ 2 = 0.532 Ans.
ρ r1 cm
3

T
3.54 For ethanol: Tc := 513.9⋅ K T := 453.15⋅ K Tr := Tr = 0.882
Tc

P
Pc := 61.48⋅ bar P := 200⋅ bar Pr := Pr = 3.253
Pc
3
cm gm
Vc := 167⋅ molwt := 46.069⋅
mol mol

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 ρr
From Fig. 3.16: ρ r := 2.28 ρ = ρ r⋅ ρ c =
Vc

ρr gm
ρ := ρ = 0.629 Ans.
Vc 3
cm
molwt

3.55 For ammonia:

T
Tc := 405.7⋅ K T := 293.15⋅ K Tr := Tr = 0.723
Tc

P
Pc := 112.8⋅ bar P := 857⋅ kPa Pr := Pr = 0.076
Pc
3
cm
Vc := 72.5⋅ Zc := 0.242 ω := 0.253
mol

⎡( 1−Tr) 0.2857⎤ 3
Vliquid := Vc⋅ Zc⎣ ⎦ cm
Eq. (3.72): Vliquid = 27.11
mol
0.422
B0 := 0.083 −
1.6 B0 = −0.627
Tr

0.172
B1 := 0.139 − B1 = −0.534
4.2
Tr

3
R⋅ T Tc
Vvapor :=
P
(
+ B0 + ω ⋅ B1 ⋅ R⋅ )
Pc
Vvapor = 2616
cm
mol

3
cm
∆V := Vvapor − Vliquid ∆V = 2589 Ans.
mol

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 Alternatively, use Tables E.1 & E.2 to get the vapor volume:

Z0 := 0.929 Z1 := −0.071 Z := Z0 + ω ⋅ Z1 Z = 0.911

3
Z⋅ R ⋅ T cm
Vvapor := Vvapor = 2591
P mol
3
cm
∆V := Vvapor − Vliquid ∆V = 2564 Ans.
mol

3.58 10 gal. of gasoline is equivalent to 1400 cu ft. of methane at 60 degF and 1

atm. Assume at these conditions that methane is an ideal gas:
3
ft ⋅ atm
R = 0.7302 T := 519.67⋅ rankine P := 1⋅ atm
lbmol⋅ rankine

3 P⋅ V
V := 1400⋅ ft n := n = 3.689 lbmol
R⋅ T
For methane at 3000 psi and 60 degF:
T
Tc := 190.6⋅ 1.8⋅ rankine T := 519.67⋅ rankine Tr := Tr = 1.515
Tc

P
Pc := 45.99⋅ bar P := 3000⋅ psi Pr := Pr = 4.498
Pc
ω := 0.012

From Tables E.3 & E.4:

Z0 := 0.819 Z1 := 0.234 Z := Z0 + ω ⋅ Z1 Z = 0.822

Z⋅ n⋅ R⋅ T 3
Vtank := Vtank = 5.636 ft Ans.
P

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 3.59 T := 25K P := 3.213bar
Calculate the effective critical parameters for hydrogen by equations (3.58)
and (3.56)
43.6
Tc := ⋅K Tc = 30.435 K
21.8K
1+
2.016T

20.5
Pc := ⋅ bar Pc = 10.922 bar
44.2K
1+
2.016T
ω := 0

P T
Pr := Pr = 0.294 Tr := Tr = 0.821
Pc Tc

3
R⋅ T cm
Initial guess of volume: V := V = 646.903
P mol

Use the generalized Pitzer correlation

0.422 0.172
B0 := 0.083 − B0 = −0.495 B1 := 0.139 − B1 = −0.254
1.6 4.2
Tr Tr
Pr
(
Z := 1 + B0 + ω ⋅ B1 ⋅ ) Tr
Z = 0.823 Ans. Experimental: Z = 0.7757

For Redlich/Kwong EOS:

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748 Table 3.1

Ψ ⋅ α ( Tr )
α ( Tr) := Tr q ( Tr) :=
− 0.5
Table 3.1 Eq. (3.54)
Ω ⋅ Tr
Ω ⋅ Pr
β ( Tr , Pr) := Eq. (3.53)
Tr

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 Calculate Z Guess: Z := 0.9

Given Eq. (3.52)

Z − β ( T r , Pr )
Z = 1 + β ( T r , Pr ) − q ( T r ) ⋅ β ( T r , Pr ) ⋅
(
Z ⋅ Z + β ( T r , Pr ) )
Z := Find ( Z) Z = 0.791 Ans. Experimental: Z = 0.7757

3.61 For methane: ω := 0.012 Tc := 190.6K Pc := 45.99bar

T := ⎡⎢( 60 − 32) ⋅
At standard condition:
5 ⎤
+ 273.15⎥ K T = 288.706 K
⎣ 9 ⎦
Pitzer correlations: P := 1atm
T P
Tr := Tr = 1.515 Pr := Pr = 0.022
Tc Pc
0.422 0.172
B0 := 0.083 − B0 = −0.134 B1 := 0.139 − B1 = 0.109
1.6 4.2
Tr Tr
Pr Pr
Z0 := 1 + B0⋅ Z0 = 0.998 Z1 := B1⋅
Tr Tr Z1 = 0.00158

3
Z⋅ R⋅ T m
Z := Z0 + ω ⋅ Z1 Z = 0.998 V1 := V1 = 0.024
P mol

T := ⎡⎢( 50 − 32) ⋅
(a) At actual condition:
5 ⎤
+ 273.15⎥ K P := 300psi
⎣ 9 ⎦
Pitzer correlations:
T = 283.15 K
T P
Tr := Tr = 1.486 Pr := Pr = 0.45
Tc Pc

0.422
B0 := 0.083 − B0 = −0.141
1.6
Tr

0.172
B1 := 0.139 − B1 = 0.106
4.2
Tr

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 Pr Pr
Z0 := 1 + B0⋅ Z0 = 0.957 Z1 := B1⋅ Z1 = 0.0322
Tr Tr

3
Z⋅ R⋅ T m
Z := Z0 + ω ⋅ Z1 Z = 0.958 V2 := V2 = 0.00109
P mol

3 V2 3
6 ft 6 ft
q1 := 150⋅ 10 q2 := q1⋅ q2 = 6.915 × 10 Ans.
day V1 day

q1
(b) n1 := 3 kmol
V1 n1 = 7.485 × 10 Ans.
hr

π 2 2
(c) D := 22.624in A := D A = 0.259 m
4
q2 m
u := u = 8.738 Ans.
A s

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 ⎛ 0.012 ⎞ ⎛ 0.286 ⎞
3.62 ⎜ ⎜ Use the first 29 components in Table B.1
⎜ 0.087 ⎟ ⎜ 0.281 ⎟ sorted so that ω values are in ascending
⎜ 0.1 ⎟ ⎜ 0.279 ⎟ order. This is required for the Mathcad
⎜ ⎟ ⎜ ⎟ slope and intercept functions.
⎜ 0.140 ⎟ ⎜ 0.289 ⎟
⎜ 0.152 ⎟ ⎜ 0.276 ⎟
⎜ ⎟ ⎜ ⎟
⎜ 0.181 ⎟ ⎜ 0.282 ⎟
⎜ 0.187 ⎟ ⎜ 0.271 ⎟
⎜ ⎟ ⎜ ⎟
⎜ 0.19 ⎟
⎜ 0.267 ⎟
⎜ 0.191 ⎟ ⎜ 0.277 ⎟
⎜ ⎟ ⎜ ⎟
0.194 0.275
⎜ ⎟ ⎜ ⎟
⎜ 0.196 ⎟ ⎜ 0.273 ⎟
⎜ 0.2 ⎟ ⎜ 0.274 ⎟
⎜ ⎟ ⎜ ⎟
⎜ 0.205 ⎟ ⎜ 0.273 ⎟
⎜ 0.21 ⎟ ⎜ 0.273 ⎟
⎜ ⎟ ⎜ ⎟
ω := ⎜ 0.21 ⎟ ZC := ⎜ 0.271 ⎟
⎜ 0.212 ⎟ ⎜ 0.272 ⎟ ( )
m := slope ω , ZC = ( −0.091)
⎜ ⎟ ⎜ ⎟
⎜ 0.218 ⎟ ⎜ 0.275 ⎟ (
b := intercept ω , ZC = ( 0.291))
⎜ 0.23 ⎟ ⎜ 0.272 ⎟
⎜ ⎟ ⎜ ⎟ ( )
r := corr ω , ZC = ( −0.878)
2
r = 0.771
⎜ 0.235 ⎟ ⎜ 0.269 ⎟
⎜ 0.252 ⎟ ⎜ 0.27 ⎟
⎜ ⎟ ⎜ ⎟
⎜ 0.262 ⎟ ⎜ 0.264 ⎟ 0.29
⎜ 0.28 ⎟ ⎜ 0.265 ⎟ ZC
⎜ ⎟ ⎜ ⎟ 0.28
⎜ 0.297 ⎟ ⎜ 0.256 ⎟ m⋅ ω+b 0.27
⎜ 0.301 ⎟ ⎜ 0.266 ⎟
⎜ ⎟ ⎜ ⎟ 0.26
⎜ 0.302 ⎟ ⎜ 0.266 ⎟
⎜ 0.303 ⎟ ⎜ 0.263 ⎟ 0.25
0 0.1 0.2 0.3 0.4
⎜ ⎟ ⎜ ⎟
ω
⎜ 0.31 ⎟
⎜ 0.263 ⎟
⎜ 0.322 ⎟ ⎜ 0.26 ⎟ The equation of the line is: Ans.
⎜ ⎜ Zc = 0.291 − 0.091ω
⎝ 0.326 ⎠ ⎝ 0.261 ⎠
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 7 5 Cp
3.65 Cp := R Cv := R γ := γ = 1.4
2 2 Cv
T1 := 298.15K P1 := 1bar

P2 := 5bar

T3 := T1 P3 := 5bar

Step 1->2 Adiabatic compression

γ −1
γ
⎛ P2 ⎞
T2 := T1⋅ ⎜ T2 = 472.216 K
⎝ P1 ⎠
∆U12 := Cv⋅ ( T2 − T1)
kJ
∆U12 = 3.618 Ans.
mol
∆H12 := Cp⋅ ( T2 − T1) kJ
∆H12 = 5.065 Ans.
mol
kJ kJ
Q12 := 0 Q12 = 0 Ans.
mol mol

kJ
W12 := ∆U12 W12 = 3.618 Ans.
mol
Step 2->3 Isobaric cooling

∆U23 := Cv⋅ ( T3 − T2)

kJ
∆U23 = −3.618 Ans.
mol

∆H23 := Cp⋅ ( T3 − T2)

kJ
∆H23 = −5.065 Ans.
mol
kJ
Q23 := ∆H23 Q23 = −5.065 Ans.
mol

W23 := −R⋅ ( T3 − T2)

kJ
W23 = 1.447 Ans.
mol
Step 3->1 Isothermal expansion

∆U31 := Cv⋅ ( T1 − T3)

kJ
∆U31 = 0 Ans.
mol

∆H31 := Cp⋅ ( T1 − T3)

kJ Ans.
∆H31 = 0
mol

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 ⎛ P1 ⎞ kJ
Q31 := −R⋅ T3⋅ ln ⎜ Q31 = 3.99 Ans.
⎝ P3 ⎠ mol
kJ
W31 := −Q31 W31 = −3.99 Ans.
mol
For the cycle
kJ
Qcycle := Q12 + Q23 + Q31 Qcycle = −1.076 Ans.
mol

kJ
Wcycle := W12 + W23 + W31 Wcycle = 1.076 Ans.
mol

Now assume that each step is irreversible with efficiency: η := 80%

Step 1->2 Adiabatic compression

W12 kJ
W12 := W12 = 4.522 Ans.
η mol

kJ
Q12 := ∆U12 − W12 Q12 = −0.904 Ans.
mol
Step 2->3 Isobaric cooling

W23 kJ
W23 := W23 = 1.809 Ans.
η mol
kJ
Q23 := ∆U23 − W23 Q23 = −5.427 Ans.
mol
Step 3->1 Isothermal expansion
kJ
W31 := η ⋅ W31 W31 = −3.192 Ans.
mol
kJ
Q31 := ∆U31 − W31 Q31 = 3.192 Ans.
mol
For the cycle
kJ
Qcycle := Q12 + Q23 + Q31 Qcycle = −3.14 Ans.
mol
kJ
Wcycle := W12 + W23 + W31 Wcycle = 3.14
mol Ans.

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 3.67 a) PV data are taken from Table F.2 at pressures above 1atm.

⎛ 125 ⎞ ⎛ 2109.7 ⎞
⎜ ⎜
⎜ 150 ⎟ ⎜ 1757.0 ⎟
⎜ 175 ⎟ ⎜ 1505.1 ⎟
⎜ ⎟ ⎜ ⎟
1316.2 ⎟ cm3
P := ⎜
200 ⎟ ⎜
kPa V := ⋅ T := ( 300 + 273.15)K
⎜ 225 ⎟ ⎜ 1169.2 ⎟ gm
⎜ ⎟ ⎜ ⎟
⎜ 250 ⎟ ⎜ 1051.6 ⎟ M := 18.01
gm
⎜ 275 ⎟ ⎜ 955.45 ⎟ mol
⎜ ⎜
⎝ 300 ⎠ ⎝ 875.29 ⎠
⎯⎯⎯ → ⎯⎯→
P⋅ V ⋅ M 1
Z := ρ := i := 0 .. 7
R⋅ T V⋅ M
If a linear equation is fit to the points then the value of B is the y-intercept.
Use the Mathcad intercept function to find the y-intercept and hence, the
value of B
3
Zi − 1 cm
Yi := Xi := ρ i B := intercept ( X , Y) B = −128.42 Ans.
ρi mol
6
5 cm
A := slope ( X , Y) A = 1.567 × 10
2
mol

mol − 5 mol − 5 mol

X := 0 , 10 ⋅ .. 8⋅ 10 ⋅
3 3 3
cm cm cm

Below is a plot of the data along with the linear fit and the extrapolation to
the y-intercept.

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 115

120
(Z-1)/p

125

130
2 .10 4 .10 6 .10 8 .10
5 5 5 5
0
p
(Z-1)/p
Linear fit

b) Repeat part a) for T = 350 C

PV data are taken from Table F.2 at pressures above 1atm.

⎛ 125 ⎞ ⎛ 2295.6 ⎞
⎜ ⎜
⎜ 150 ⎟ ⎜ 1912.2 ⎟
⎜ 175 ⎟ ⎜ 1638.3 ⎟
⎜ ⎟ ⎜ ⎟
1432.8 ⎟ cm3
P := ⎜
200 ⎟ ⎜
kPa V := ⋅ T := ( 350 + 273.15)K
⎜ 225 ⎟ ⎜ 1273.1 ⎟ gm
⎜ ⎟ ⎜ ⎟
⎜ 250 ⎟ ⎜ 1145.2 ⎟ M := 18.01
gm
⎜ 275 ⎟ ⎜ 1040.7 ⎟ mol
⎜ ⎜
⎝ 300 ⎠ ⎝ 953.52 ⎠
⎯⎯⎯ → ⎯⎯→
P⋅ V ⋅ M 1
Z := ρ := i := 0 .. 7
R⋅ T V⋅ M
If a linear equation is fit to the points then the value of B is the y-intercept.
Use the Mathcad intercept function to find the y-intercept and hence, the
value of B
3
Zi − 1 cm
Yi := Xi := ρ i B := intercept ( X , Y) B = −105.899 Ans.
ρi mol

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 6
5 cm
A := slope ( X , Y) A = 1.784 × 10
2
mol

mol − 5 mol − 5 mol

X := 0 , 10 ⋅ .. 8⋅ 10 ⋅
3 3 3
cm cm cm
Below is a plot of the data along with the linear fit and the extrapolation to
the y-intercept.

90

95
(Z-1)/p

100

105

110
2 .10 4 .10 6 .10 8 .10
5 5 5 5
0
p
(Z-1)/p
Linear fit

c) Repeat part a) for T = 400 C

PV data are taken from Table F.2 at pressures above 1atm.

⎛ 125 ⎞ ⎛ 2481.2 ⎞
⎜ ⎜
⎜ 150 ⎟ ⎜ 2066.9 ⎟
⎜ 175 ⎟ ⎜ 1771.1 ⎟
⎜ ⎟ ⎜ ⎟
1549.2 ⎟ cm3
P := ⎜
200 ⎟ ⎜
kPa V := ⋅ T := ( 400 + 273.15)K
⎜ 225 ⎟ ⎜ 1376.6 ⎟ gm
⎜ ⎟ ⎜ ⎟
⎜ 250 ⎟ ⎜ 1238.5 ⎟ M := 18.01
gm
⎜ 275 ⎟ ⎜ 1125.5 ⎟ mol
⎜ ⎜
⎝ 300 ⎠ ⎝ 1031.4 ⎠
70

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 ⎯⎯⎯ → ⎯⎯→
P⋅ V ⋅ M 1
Z := ρ := i := 0 .. 7
R⋅ T V⋅ M
If a linear equation is fit to the points then the value of B is the
y-intercept.
Use the Mathcad intercept function to find the y-intercept and hence,
the value of B
3
Zi − 1 cm
Yi := Xi := ρ i B := intercept ( X , Y) B = −89.902 Ans.
ρi mol
6
5 cm
A := slope ( X , Y) A = 2.044 × 10
2
mol

mol − 5 mol − 5 mol

X := 0 , 10 ⋅ .. 8⋅ 10 ⋅
3 3 3
cm cm cm
Below is a plot of the data along with the linear fit and the extrapolation to
the y-intercept.

70

75
(Z-1)/p

80

85

90
2 .10 4 .10 6 .10 8 .10
5 5 5 5
0
p
(Z-1)/p
Linear fit

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 ( Z − 1) ⋅ Z⋅ Tr Pr
3.70 Create a plot of vs
Pr Z⋅ Tr
Data from Appendix E at Tr = 1

⎛ 0.01 ⎞ ⎛ 0.9967 ⎞
⎜ 0.05 ⎜ 0.9832
⎜ ⎟ ⎜ ⎟
⎜ 0.10 ⎟ ⎜ 0.9659 ⎟
Pr := ⎜ 0.20 ⎟ Z := ⎜ 0.9300 ⎟ Tr := 1
⎜ ⎟ ⎜ ⎟
⎜ 0.40 ⎟ ⎜ 0.8509 ⎟
⎜ 0.60 ⎟ ⎜ 0.7574 ⎟
⎜ ⎜
⎝ 0.80 ⎠ ⎝ 0.6355 ⎠
⎯⎯→ ⎯⎯⎯⎯⎯ →
Pr ( Z − 1) ⋅ Z⋅ Tr
X := Y :=
Z⋅ Tr Pr

Create a linear fit of Y vs X

Slope := slope ( X , Y) Slope = 0.033

Intercept := intercept ( X , Y) Intercept = −0.332

Rsquare := corr ( X , Y) Rsquare = 0.9965

0.28

Y 0.3

Slope⋅ X+Intercept
0.32

0.34
0 0.2 0.4 0.6 0.8 1 1.2 1.4
X

The second virial coefficient (Bhat) is the value when X -> 0

Bhat := Intercept Bhat = −0.332 Ans.

0.422
By Eqns. (3.65) and (3.66) B0 := 0.083 − B0 = −0.339 Ans.
1.6
Tr
These values differ by 2%.

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 3.71 Use the SRK equation to calculate Z
T
Tc := 150.9⋅ K T := ( 30 + 273.15) ⋅ T
Kr := Tr = 2.009
Tc
P
Pc := 48.98⋅ bar P := 300⋅ bar Pr := Pr = 6.125
Pc
ω := 0.0

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748 Table 3.1

2
⎡ ⎛ 1⎞ ⎤

α ( Tr , ω ) := ⎣ 1 + ( 0.480 + 1.574ω − 0.176ω ) ⋅ ⎝ 1 − Tr ⎠ ⎦

⎢ 2 ⎜ 2 ⎥
Table 3.1

q ( Tr) :=
(
Ψ ⋅ α Tr , ω ) Eq. (3.54) β ( Tr , Pr) :=
Ω ⋅ Pr
Eq. (3.53)
Ω ⋅ Tr Tr

Calculate Z Guess: Z := 0.9

Given Eq. (3.52)

Z − β ( T r , Pr )
Z = 1 + β ( T r , Pr ) − q ( T r ) ⋅ β ( T r , Pr ) ⋅
( Z + ε ⋅ β ( T r , Pr ) ) ⋅ ( Z + σ ⋅ β ( T r , Pr ) )
3
Z⋅ R ⋅ T cm
Z := Find ( Z) Z = 1.025 V := V = 86.1 Ans.
P mol
This volume is within 2.5% of the ideal gas value.

3.72 After the reaction is complete, there will be 5 moles of C 2H2 and 5 moles of
Ca(OH)2.

First calculate the volume available for the gas.

3
3 cm 3
n := 5mol Vt := 0.4⋅ 1800⋅ cm − 5⋅ mol⋅ 33.0⋅ Vt = 555 cm
mol
3
Vt cm
V := V = 111
n mol

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 Use SRK equation to calculate pressure.
T
Tc := 308.3⋅ K T := ( 125 + 273.15) ⋅ K Tr := Tr = 1.291
Tc
Pc := 61.39⋅ bar ω := 0.0

σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.42748 Table 3.1

2
⎡ ⎛ 1⎞ ⎤

α ( Tr , ω ) := ⎣ 1 + ( 0.480 + 1.574ω − 0.176ω ) ⋅ ⎝ 1 − Tr ⎠ ⎦

⎢ 2 ⎜ 2 ⎥
Table 3.1

q ( Tr) :=
(
Ψ ⋅ α Tr , ω ) Eq. (3.54)
Ω ⋅ Tr

a := Ψ ⋅
( )
α Tr , ω ⋅ R ⋅ Tc
2 2
Eq. (3.45) b := Ω ⋅
R⋅ Tc
Eq. (3.46)
Pc Pc
3
3 bar⋅ cm 3
a = 3.995 m cm
2 b = 36.175
mol mol
R⋅ T a
P := − P = 197.8 bar Ans.
V − b V ⋅ ( V + b)

3.73 mass := 35000kg T := ( 10 + 273.15)K

gm
ω := 0.152 Tc := 369.8K Pc := 42.48bar M := 44.097
mol
3
cm mass 5
Zc := 0.276 Vc := 200.0 n := n = 7.937 × 10 mol
mol M

a) Estimate the volume of gas using the truncated virial equation

T P
Tr := Tr = 0.766 P := 1atm Pr :=
Tc Pc

0.422 0.172
B0 := 0.083 − Eq. (3-65) B1 := 0.139 − Eq. (3-66)
1.6 4.2
Tr Tr
B0 = −0.564 B1 = −0.389

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 Pr
Z := 1 + ( B0 + ω ⋅ B1) ⋅ Z = 0.981
Tr

Z⋅ n⋅ R⋅ T 7 3 3
Vt := Vt = −2.379 × 10 m m
P
3
This would require a very large tank. If the 6
D := ⋅ Vt D = 32.565 m
tank were spherical the diameter would be: π
b) Calculate the molar volume of the liquid with the Rackett equation(3.72)
(1−Tr)0.2857 3
Vliq := Vc⋅ Zc cm
Vliq = 85.444
mol
P
P := 6.294atm Pr := Pr = 0.15
Pc
Pr
Z := 1 + ( B0 + ω ⋅ B1) ⋅
Tr Z = 0.878

Z⋅ R ⋅ T 3
Vvap := 3 cm
P Vvap = 3.24 × 10
mol
Guess: Vtank := 90%⋅ Vliq⋅ n

Vtank Vtank
Given 90%⋅ + 10% = n Vtank := Find ( Vtank)
Vliq Vvap

3
Vtank = 75.133 m

This would require a small tank. If the tank 3

6
were spherical, the diameter would be: D := ⋅ Vtank D = 5.235 m
π

Although the tank is smaller, it would need to accomodate a pressure of 6.294

atm (92.5 psi). Also, refrigeration would be required to liquify the gaseous
propane stream.

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