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Thermodynamics
Introduction
The thermodynamic approach was developed in the nineteenth century
for a better understanding of the change in the energy in steam engines.
Certain principles were developed, known as the first and second laws
of thermodynamics, to mathematically correlate the changes in heat
and energy during a particular process. An understanding of the above
is extremely important for all branches of science and engineering. The
mathematical correlations developed help us to understand how the
physical properties and energies are changed during operations such as
compression, expansion, and so on.
Force
Force is derived from Newtons second law as a product of mass and acceleration. The SI unit of force is N. Mathematically
F = ma
(2.1)
750 N on Earth (a = 9.81 m/s2), his mass on Earth will be 76.45 kg and his
weight on the moon will be 127.67 N (assuming that the acceleration on
the moon is 1.67 m/s2).
(2.2)
(2.3)
v 2 v12
mv 2
W = m 2
=
2
2
(2.4)
Integrating
1
mv 2
2
(2.5)
(2.6)
(2.7)
Chapter two:
Thermodynamics
versa. Alternatively, energy can exist in different forms and the total
quantity of energy is always constant. If energy disappears in one form, it
will appear in some other form simultaneously.
According to the first law of thermodynamics, the relationship among
internal energy, heat, and work in a closed system can be expressed mathematically as
dU = dQ + dW
(2.8)
Phase rule
In a heterogeneous system, phase rule defines how the degree of freedom
(F) relates to the number of components (C) and the number of phases (P),
such as
F=CP+2
(2.9)
Reversible process
A system can change from one state to another through either a reversible or an irreversible process. In a reversible process, the change occurs
slowly in minute quantities till the total specified change happens.
If an expansion is carried out from an initial pressure P1 to a final
pressure P2 (volume from V1 to V2), the reversible work (Wr) and irreversible work (Wir) done at constant temperature are
Wr = RT ln
V2
P
= RT ln 1
V1
P2
Wir = P2 (V2 V1 ) = RT 1 2
P1
(2.10)
(2.11)
RT
(P1 P2 )2
P1P2
(2.12)
(2.13)
dH = dU + PdV + VdP
(2.14)
In differential form
(2.15a)
Chapter two:
Thermodynamics
5
H
CP =
T P
(2.15b)
The values of two specific heats are not the same, and the relationship
between the two values can be expressed as
U
H
CP CV =
T P T V
U
U
V
=
+ P
T P
T P T
T V
U
U
U V
V
=
+
+ P
T V V T T P
T P T V
(Since U = f(T,V))
U
V
=
+ P
V T
T P
For ideal gas, (U/V)T = 0
Therefore
R
V
CP CV = P
= P*
=R
T P
P
(2.16)
Isothermal process
An isothermal process is a process when the temperature remains constant. The work done to increase an ideal gas pressure from P1 to P2 is
defined as
PV = constant
W = RT ln
P2
P1
(2.17)
Adiabatic process
An adiabatic process is the process when there is no heat transfer between
the system and the surrounding area (dQ = 0). For this case, the work done
RT1 P2
1
1 P1
W =
(2.18)
Example 2.2
1 kmol air is compressed from 100 kPa and 25C to 500 kPa. Calculate
the work done if the compression is (a) isothermal and (b) adiabatic.
The ratio of specific heats for air is 1.4.
SOLUTION
a. The work done for an isothermal process
W = RT ln
P2
= 8.314 * 298 * 1.609 = 3987.5 kJ
P1
8.314 * 298
(1.584 1) = 3616.1 kJ
0.4
Equation of state
Boyles law and Charless law
We can assume a cubical box with each side of length l (as shown in Figure
2.1) and whose three axes are x, y, and z. The velocity v can be defined as
v 2 = x 2 + y 2 + z2
y
B
c
x
(2.19)
Chapter two:
Thermodynamics
2mNv 2
l
(2.20)
1 mNv 2
F
=
6l 2
3 V
(2.21a)
or
PV =
1
mNv 2
3
(2.21b)
where
V = volume of the cube
Now
PV =
2
1
N * mv 2
3
2
For a given mass of gas, 2/3 N and mv2 (kinetic energy) are constant
if the temperature is constant. Otherwise, PV is constant when the temperature is constant. This is Boyles law.
Again, at constant pressure, V/T is constant, which is Charless law.
Combining Boyles and Charless laws
PV = RT
where
R = universal gas constant
(2.22)
(2.23)
The first equation of state (EOS) was developed by J.D. van der Waals
in 1873 and presented as [1]
a
P + 2 (V b) = RT
V
(2.24)
where the values of a,b typically depend on the pressure and temperature
conditions. Changing the values to zero, the equation will modify into the
equation of an ideal gas.
Various EOSs were developed to establish calculation procedures for
a and b. Out of a large number of EOSs, the following two are extensively
used in process engineering calculations:
PengRobinson (PR) [2]
SoaveRedlichKwong (SRK) [3]
Acentric factor
One important parameter presented in the EOS is the acentric factor .
The acentric factor is used to correlate physical and thermodynamic properties. Mathematically, the acentric factor is defined as [4]
= log pr* 1.000
(2.26)
Chapter two:
Thermodynamics
SRK
RT
a
V b V (V + b) + b(V b)
Z 3 (1 B)Z 2 + ( A 2B 3B2 )Z
P=
RT
a
V b V (V + b)
Z3 Z2 + (A B B2)Z
AB = 0
Equation
number
(2.25a)
(2.25b)
( AB B2 B3 ) = 0
where
b=
x b
x b
i i
i i
i =1
i =1
bi = 0.077796
a=
i =1
(2.25c)
RTci
Pci
xi ai 0.5
0.08664
RTci
Pci
xi ai
i =1
0.5
acii
ai = acii
(2.25d)
(2.25e)
(2.25f)
(RTci )2
Pci
(2.25g)
0i .5 = 1 + mi (1 T 0ri.5 )
1 + mi (1 T ri0.5 )
(2.25h)
(2.25i)
aci = 0.457235
(RTci )2
Pci
0.42747
A=
aP
(RT )2
aP
(RT )2
(2.25j)
B=
bP
RT
bP
RT
(2.25k)
Note: T = absolute temperature, P = absolute pressure, V = specific volume, Z = compressibility, Tc = critical temperature, Pc = critical pressure, Tr = reduced temperature,
= acentric factor, a,b = parameters used in the equations, a(T) = parameter used in
the equations, ac = value of a(T) at T = Tc, = correction factor, a/ac, m = slope of 0.5
against Tr0.5, i = component i in the mixture, N = number of components.
10
where
pr* = reduced vapor pressure, p*/pc
p* = vapor pressure at T = 0.7Tc, kPaA
pc = critical pressure, kPaA
T = temperature, K
Tc = critical temperature, K
For hydrocarbon mixtures, the acentric factor is calculated as
N
x
i
(2.27)
i =1
where
N = number of components
i = acentric factor of component i
xi = mole fraction of component i
Other important factors used to establish the physical and thermodynamic properties of hydrocarbon mixtures are the Watson characterization factor K and the critical compressibility factor zc. Table 2.2 presents
the values of the acentric factor, the Watson characterization factor, and
the critical compressibility factor. A complete list is available in the API
Technical Data Book [4].
B
T+C
(2.28)
where
P = vapor pressure, mmHg
T = temperature, K
A,B,C = constants in the Antoine equation
For the commonly used hydrocarbon vapor, the values of constants A,
B, and C along with critical pressures and temperatures are presented in
Table 2.3. A more complete list is available in the literature [1,5].
Chapter two:
Thermodynamics
11
Components
Acentric
factor ()
Hydrogen
Nitrogen
Oxygen
Carbon monoxide
Carbon dioxide
Sulfur dioxide
Hydrogen sulfide
Water
Ammonia
Nonhydrocarbons
0.2153
0.04
0.0218
0.0663
0.23894
0.2451
0.081
0.344
0.252
Methane
Ethane
Propane
n-Butane
i-Butane
n-Pentane
i-Pentane
2,2-Dimethylpropane
n-Hexane
i-Hexane
3-Methylpentane
2,2-Dimethylbutane
2,3-Dimethylbutane
n-Heptane
i-Heptane
3-Methylhexane
3-Ethylpentane
2,2-Dimethylpentane
2,3-Dimethylpentane
2,4-Dimethylpentane
3,3-Dimethylpentane
2,2,3-Trimethylbutane
n-Octane
Paraffins
0.011498
0.0986
0.1524
0.201
0.18479
0.25389
0.2224
0.1964
0.3007
0.2781
0.2773
0.2339
0.2476
0.3494
0.3282
0.3216
0.3094
0.2879
0.2923
0.3018
0.2672
0.2503
0.3962
19.54
19.49
14.69
13.50
13.78
13.03
13.01
13.36
12.78
12.82
12.65
12.77
12.62
12.68
12.72
12.55
12.36
12.60
12.35
12.72
12.42
12.38
12.68
Critical
compressibility
factor (zc)
0.305
0.292
0.288
0.295
0.274
0.269
0.284
0.229
0.242
0.288
0.284
0.280
0.274
0.282
0.269
0.270
0.269
0.264
0.267
0.273
0.272
0.269
0.263
0.261
0.255
0.268
0.267
0.256
0.265
0.273
0.266
0.259
continued
12
Critical
compressibility
factor (zc)
Components
Acentric
factor ()
i-Octane
n-Nonane
n-Decane
0.3768
0.4368
0.4842
12.64
12.64
12.64
0.261
0.255
0.249
Cyclopropane
Cyclobutane
Cyclopentane
Methylcyclopentane
Ethylcyclopentane
Cyclohexane
Methylcyclohexane
Ethylcyclohexane
Cyclooctane
Napthenes
0.1348
11.93
0.1866
11.45
0.1943
10.94
0.2302
11.32
0.2715
11.39
0.2149
11.00
0.2350
11.31
0.2455
11.36
0.2536
10.89
0.274
0.274
0.273
0.272
0.269
0.273
0.269
0.270
0.270
Ethylene
Propylene
1-Butene
cis-2-Butene
trans-2-Butene
i-Butylene
1-Pentene
cis-2-Pentene
trans-2-Pentene
1-Hexene
cis-2-Hexene
trans-2-Hexene
1-Heptene
trans-2-Heptene
1-Octene
trans-2-Octene
1-Nonene
1-Decene
0.0852
0.1424
0.1867
0.2030
0.2182
0.1893
0.2330
0.2406
0.2373
0.2800
0.2722
0.2613
0.3310
0.3389
0.3747
0.3384
0.4171
0.4645
Olefins
14.21
13.04
12.61
12.93
13.01
12.65
12.48
12.61
12.50
12.30
12.45
12.41
12.39
12.40
12.36
12.42
12.46
0.277
0.275
0.276
0.272
0.274
0.275
0.270
0.279
0.279
0.265
0.266
0.267
0.262
0.256
0.256
0.260
0.249
0.247
Chapter two:
Thermodynamics
13
Critical
compressibility
factor (zc)
Components
Acentric
factor ()
Propadiene
1,2-Butadiene
1,3-Butadiene
1,2-Pentadiene
1,3-Pentadiene
2,3-Pentadiene
0.1594
0.2509
0.1932
0.2235
0.0837
0.2194
12.58
12.16
12.51
11.90
12.21
11.91
0.271
0.267
0.270
0.256
0.285
0.253
Acetylene
Methylacetylene
Ethylacetylene
Acetylenes
0.1873
16.72
0.2161
12.34
0.0500
12.14
0.271
0.276
0.270
Benzene
Toluene
Ethylbenzene
o-Xylene
m-Xylene
p-Xylene
n-Propylbenzene
i-Propylbenzene
n-Butylbenzene
i-Butylbenzene
Napthalene
Aromatics
0.2108
0.2641
0.3036
0.3127
0.3260
0.3259
0.3462
0.3377
0.3917
0.3811
0.3019
0.271
0.264
0.263
0.263
0.259
0.260
0.265
0.262
0.261
0.256
0.269
Diolefins
9.74
10.11
10.33
10.27
10.41
10.44
10.59
10.54
10.82
10.84
9.32
Source: Adapted from Technical Data BookPetroleum Refining, 4th ed., American Petroleum
Institute, Washington, D.C., 1982.
(2.29)
14
Table 2.3 Values of Antoine Constants and Critical Pressures and Temperatures
Components
Constant in Antoine
equation
Temperature
limits (C)
Min
Max
Critical conditions
Pressure Temperature
(kPa)
(K)
Methane
15.2243
597.84
7.16
180
153
4640.7
190.7
Ethane
Propane
n-Butane
i-Butane
n-Pentane
n-Hexane
n-Heptane
n-Octane
n-Nonane
n-Decane
Carbon
monoxide
Carbon
dioxide
Hydrogen
sulfide
Nitrogen
Oxygen
Hydrogen
Water
15.6637
15.726
15.6782
15.5381
15.8333
15.8366
15.8737
15.9426
15.9671
16.0114
14.3686
1511.42
1872.46
2154.9
2032.73
2477.07
2697.55
2911.32
3120.29
3291.45
2456.8
530.22
17.16
25.16
34.42
33.15
39.94
48.78
56.51
63.63
71.33
78.67
13.15
143
109
78
86
53
28
3
19
39
57
210
74
24
17
7
57
97
127
152
179
203
165
4883.9
4256.7
3796.6
3647.6
3375.1
3031.6
2736.8
2490
2290
2110
3499
305.4
369.9
425.2
408.1
469.6
507.9
540.2
568.7
594.6
617.7
132.9
22.5898
3103.39
0.16
119
69
7370
304.1
16.1040
1768.69
26.06
83
43
9007.8
373.6
14.9542
15.4075
13.6333
18.3036
588.72
734.55
164.9
3816.44
6.6
6.45
3.19
46.13
219
210
259
11
183
173
248
168
3394.4
5043
1313
22,120
126.2
154.6
33.19
647.3
P
B Z
(2.30)
f
Z + 2.414B
A
= Z 1 ln(Z B)
ln
P
2 2B Z 0.414B
(2.31)
ln
PR EOS
ln
Chapter two:
Thermodynamics
15
2697.55
= 5.29806
304.75 48.78
or
P = 199.95 mmHg = 26.66 kPa
Use PR EOS
Critical pressure = 3025 kPa
Critical temperature = 507.6 K
Acentric factor = 0.3047
Temperature = 304.75 K
Parameters are calculated as
ac = 0.457235
(8.314 * 507.6)2
= 2692.04
3025
8.314 * 507.6
= 0.1085
3025
(2.32)
16
3777.15 * 1
= 0.0005884
(8.314 * 304.75) 2
B=
0.1085 * 1
= 0.000043
304.75 * 8.314
Chapter two:
Thermodynamics
17
Carnots cycle
Carnots cycle (Figure 2.2) can be used to explain how and to what extent
work is obtained from heat. In this cycle, the engine starts at a point A and
comes back to the same point. Alternatively, the engine must operate in
a complete cycle. Also, maximum work can be obtained when every step
operates in a reversible fashion.
In the above cycle, the following operations can be analyzed.
Operation 1: Gas is allowed to expand, isothermally and reversibly,
from point A to point B (volume changes from V1 to V2). For an ideal gas,
the heat absorbed is equal to the work done.
Q1 = RT1 ln
V2
V1
(2.33)
Operation 2: The gas is then allowed to expand from V2 to V3 adiabatically and reversibly till the temperature drops to the temperature of the
sink. Owing to the adiabatic process, the heat exchange is 0. The work
done (W1) by the gas can be calculated as
W1 = CV (T1 T2)
(2.34)
A V1
V4
V3
T1
(2.35)
V2
P
D
V4
T2
C V3
18
(2.36)
The net work (W) done by the gas in the complete cycle
W = RT1 ln
V2
V
+ CV (T1 T2 ) + RT2 ln 4 CV (T1 T2 )
V1
V3
(2.37)
V2
V
+ RT2 ln 4
V1
V3
(2.38)
or
W = RT1 ln
V2
V1
(2.39)
(2.40)
W = Q1 1 2
T1
(2.41)
Entropy
With some extension of the above analysis, it can be concluded that a thermodynamic change defined as dQ/T is independent of the path of the
Chapter two:
Thermodynamics
19
transformation of the system. This function is called entropy and is normally denoted by S.
Mathematically, the change in entropy is measured by the ratio of
the heat change and temperature at which the heat change occurs and is
defined as
dS =
dQrev
T
(2.42)
The term dQrev indicates that the heat change occurs through a reversible process.
Sensible heat
Enthalpy is a function of temperature and pressure
H = f(T,P)
or
H
H
dH =
dT +
dP
T P
P T
or
H
dH = CP dT +
dP
P T
(2.43a)
In the above equation, the second term is zero for the following
conditions:
a. When the pressure is constant
b. When enthalpy is independent of the pressure, for example, lowpressure gas
Considering the above conditions, the change in enthalpy can be
defined as
dH = CP dT
where CP is the isobaric specific heat.
(2.43b)
20
Thermodynamic properties
The following thermodynamic properties are extremely important in all
process engineering calculations. This section will discuss the method to
estimate these thermodynamic properties.
(2.44)
where
CP = specific heat of ideal gas, kJ/(kmolK)
R = universal gas constant, kJ/(kmolK)
T = temperature, K
A,B,C,D = constants
Constants for the calculation of the specific heat of commonly used
ideal gases are presented in Table 2.4.
Example 2.4
Estimate the heat required to raise the temperature of 1 kmol methane from 100C to 400C.
Chapter two:
Thermodynamics
21
MW
Tmax (K)
B * 103
C * 106
Methane
16.043
1500
1.702
9.081
2.164
Ethane
30.070
1500
1.131
19.225
5.561
Propane
44.097
1500
1.213
28.785
8.824
n-Butane
58.123
1500
1.935
36.915
11.402
i-Butane
58.123
1500
1.677
37.853
11.945
n-Pentane
72.150
1500
2.464
45.351
14.111
n-Hexane
86.177
1500
3.025
53.722
16.791
n-Heptane
100.204
1500
3.570
62.127
19.486
n-Octane
114.231
1500
4.108
70.567
22.208
28.851
2000
3.355
0.575
Air
D * 105
0.016
Nitrogen
28.014
2000
3.280
0.593
0.040
Oxygen
31.999
2000
3.639
0.506
0.227
2.016
3000
3.249
0.422
0.083
Hydrogen sulfide
34.082
2300
3.931
1.49
0.232
Carbon monoxide
28.010
2500
3.376
0.557
0.031
Carbon dioxide
44.01
2000
5.457
1.045
1.157
Water
18.015
2000
3.47
1.45
Hydrogen
0.121
Source: Adapted from Smith, J.M., Van Ness, H.C., and Abbott, M.M., Introduction to Chemical
Engineering Thermodynamics, 6th ed., McGraw-Hill, New York, 2001.
Note: Values for other components are available in the literature [1,5,7]. Tmax is the maximum temperature, K.
SOLUTION
The heat required can be calculated as
T2
Q = dH =
C dT
P
T1
k
=R
R dT
CP
T2
T3
= R AT1 (k 1) + B 1 (k 2 1) + C 1 (k 3 1)
2
3
where
T1 = initial temperature = 373.15 K
k = temperature ratio = 673.15/373.15 = 1.804
A,B,C = constants as per Table 2.4
22
373.152
Q = 8.314 1.702 * 373.15 * 0.804 + 9.801 * 10 3
*
2
2.254 2.164 * 10 6
373.153
* 4.871
3
= 15515 kJ
(2.45)
where
CP = isobaric specific heat of the real gas, kJ/(kmolK)
C P0 = isobaric specific heat of the ideal gas, kJ/(kmolK)
R = gas constant = 8.314 kJ/(kmolK)
(C P0 CP )/R = dimensionless correction factor
The dimensionless correction factor is calculated as
0
CP0 CP CP0 CP
+ h
=
R
R
C 0 C h C 0 C 0
P
P
P
P
R
R
(2.46)
where
((C P0 CP )/R)0 = effect of the pressure for simple fluid (use Equation
2.47 to calculate)
((C P0 CP )/R)h = effect of the pressure for the heavy reference fluid
(n-octane) (use Equation 2.47 to calculate)
The pressure effect is calculated as
i
CP0 CP
T (Pr /Tr )V2 r CV
= 1+ r
+
R
R
(Pr /Vr )Tr
(2.47)
Chapter two:
Thermodynamics
23
where
1
Pr
2c
b1 + b3 /Tr2 + 2b4 /Tr3 c1 2c3 /Tr3
d
+
+ 15 3 4 2
T = V 1 +
2
Tr Vr
Vr
Vr
Vr
r Vr
r
+ 2 exp 2
Vr
Vr
Tr
c4
2B 3C 6D
Pr
V = V 2 1 + V + V 2 + V 5 + T 3V 2 3 + 5
r Tr
r
r
r
r
r r
(2.48)
2 + 2 2
Vr Vr
exp 2
Vr
(2.49)
=
2
R
Tr Vr
Tr Vr
(2.50)
where
Pr = reduced pressure
Tr = reduced temperature
Vr = reduced volume = ZTr/Pr
Z = compressibility
B = b1
b2
b
b
32 43
Tr Tr
Tr
(2.51a)
c2
c
+ 33
Tr Tr
(2.51b)
d2
Tr
(2.51c)
C = c1
D = d1 +
E=
c4
+ 1 + 1 + 2 exp 2
3
Vr
Vr
2Tr
(2.51d)
Other constants used in the above equations for both simple and
heavy reference fluids are tabulated in Table 2.5.
24
Simple uid
b1
b2
b3
b4
c1
c2
c3
c4
d1 * 104
d2 * 104
0.1181193
0.265728
0.154790
0.030323
0.0236744
0.0186984
0
0.042724
0.155488
0.623689
0.65392
0.060167
Heavy reference
uid
0.2026579
0.331511
0.027655
0.203488
0.0313385
0.0503618
0.016901
0.041577
0. 48736
0.0740336
1.226
0.03754
Ppc =
x P
i ci
(2.52)
i =1
n
Tpc =
xT
i ci
(2.53)
i =1
n
x
i
(2.54)
i =1
CP =
w C
i
pi
where
Ppc = mixtures pseudocritical pressure, kPa
Pci = critical pressure of component i, kPa
Tpc = mixtures pseudocritical temperature, K
Tci = critical temperature of component i, K
(2.55)
Chapter two:
Thermodynamics
25
n = number of components
xi = mole fraction of component i
= mixtures acentric factor
i = acentric factor of component i
CP = mixtures isobaric specific heat
CPi = isobaric specific heat of component i
wi = weight fraction of component i
Example 2.5
Estimate the isobaric specific heat for
i.
ii.
iii.
iv.
SOLUTION
i. Isobaric specific heat of ideal gas = 34.74 kJ/(kmolK)
Compressibility = 0.81698
Pr
T = 2.3698
r Vr
Pr
V = 3.4043
r Tr
i
CV
R = 0.2418
0
C P0 CP
= 1.77765
R
C P0 CP
= 1.7572
R
CP = 34.74 + 8.314 * 1.7572 = 49.35 kJ/(kmolK)
(HYSYS calculated value is 49.32 kJ/(kmolK))
ii. Isobaric specific heat of ideal gas = 56.226 kJ/(kmolK)
Compressibility = 0.77283
C P0 CP
= 1.6363
R
CP = 69.83 kJ/(kmolK)
(HYSYS calculated value is 69.98 kJ/(kmolK))
26
R
CP = 32.43 kJ/(kmolK)
(HYSYS calculated value is 32.99 kJ/(kmolK))
iv. Pseudocritical pressure = 4625.48 kPa
Pseudocritical temperature = 235.88 K
Acentric factor = 0.05354
Compressibility factor = 0.87746 (Note-1)
Isobaric specific heat of methane at 30C = 35.38 kJ/(kmolK)
Isobaric specific heat of ethane at 30C = 53.61 kJ/(kmolK)
Isobaric specific heat of nitrogen at 30C = 29.13 kJ/(kmolK)
Weight fraction of methane = 0.3064
Weight fraction of ethane = 0.5743
Weight fraction of nitrogen = 0.1193
Isobaric specific heat of ideal mixtures = 45.11 kJ/(kmolK)
CP0 CP
= 0.7559
R
CP = 51.4 kJ/(kmolK)
(HYSYS calculated value is 49.64 kJ/(kmolK), Note-1)
Note-1: The compressibility factor is calculated without considering the interaction parameters. As a result, both the compressibility factor and the isobaric specific heat of real gas
mixtures will be different from the calculated value using the
interaction parameters.
JouleThomson coefficient
If we consider a case where volume V1 of a gas at pressure P1 is allowed to
pass to a lower pressure P2, through a semipermeable membrane slowly
and reversibly, the volume at the lower pressure side will increase to V2
(V2 > V1) as shown in Figure 2.3. If we assume that the piston is frictionless
and the system is thermally insulated and there is no heat change (dQ = 0),
then the work done can be defined as
Work done by the high-pressure side = P1V1
Work done by the low-pressure side = P2V2
Chapter two:
Thermodynamics
27
V1
P1
V2
P2
(2.56)
Generally, the value of is positive, meaning that with a drop in pressure, the temperature will also drop. However, in some cases (hydrogen,
helium at room temperature), the value of is negative, meaning that
there will be an increase in temperature with a decrease in pressure.
Now, H = f(T,P)
1 H
T
T H
=
=
P H
H P P T
CP P T
or
=
1 H
CP P T
(2.57)
28
Again
RT 2 Z
H
V
=
V
T
P T
T P
P T P
where
Z = compressibility factor
The general equation of the JouleThomson coefficient can be
defined as [1]
=
RT 2 Z
CP P T P
Example 2.6
Estimate the JouleThomson cooling temperature if methane at
10,000 kPag and 20C is expanded to the atmospheric pressure.
SOLUTION
This can be calculated by reducing the pressure in steps and estimating
the temperature at the end of each step. The isobaric specific heat of a
real gas is calculated using the procedure described in Example 2.5.
The PR EOS is used for this calculation.
Let the number of steps be 50; therefore, the reduction in pressure
at the end of each step will be 200 kPa.
Constant parameters
Critical pressure = 4640.68 kPa
Critical temperature = 190.7 K
Acentric factor = 0.0115
Step 1 calculation
Calculated the value of mi (Equation 2.25i) = 0.3923
Calculated the value of aci (Equation 2.25g) = 247.67
Calculated the value of bi (Equation 2.25d) = 0.0266
Compressibility (Z) = 0.81792
Value of (Z/T)P = 0.00239
Isobaric heat capacity of a real gas = 49.35 kJ/(kmolK)
JouleThomson coefficient (Equation 2.58) = 0.00342
Drop in temperature (Equation 2.56) = 0.68C
Temperature after first step = 19.32C
The above step is repeated 50 times to calculate the final
temperature.
(2.58)
Chapter two:
Thermodynamics
29
Initial
Final
Methane
Methane
Methane
Ethane
Propane
i-Butane
Carbon dioxide
Nitrogen
Nitrogen
Nitrogen
10,000
8000
8000
3000
2000
1000
5000
8000
7000
6000
0
0
3000
0
0
0
0
0
0
2000
Initial
temperature (oC)
20
7
10
60
100
150
60
7
10
0
Final temperature
(oC)
HYSYS
Manual
32.3
60.5
39.9
29.1
78.6
141.6
8.1
30.3
8.2
10.6
32.0
61.3
40.4
30.1
78.8
141.6
6.1
30.6
8.4
10.7
(2.59)
w C
i
pi
where
CP = isobaric specific heat of mixtures
wi = weight fraction of component i
CPi = isobaric specific heat of component i
(2.60)
30
Liquids
B * 103
C * 106
Ammonia
22.626
100.75
192.71
Aniline
15.819
29.03
15.80
Benzene
0.747
67.96
37.78
1,3-Butadiene
22.711
87.96
205.79
Carbon tetrachloride
21.155
48.28
101.14
31.90
Chlorobenzene
11.278
32.86
Chloroform
19.215
42.89
83.01
Cyclohexane
9.048
141.38
161.62
Ethanol
33.866
172.60
349.17
Ethylene oxide
21.039
86.41
172.28
Methanol
13.431
51.28
131.13
n-Propanol
41.653
210.32
427.20
Sulfur trioxide
2.930
137.08
84.73
Toluene
15.133
6.79
16.35
8.712
1.25
0.18
Water
Source: Adapted from Smith, J.M., Van Ness, H.C., and Abbott, M.M., Introduction to
Chemical Engineering Thermodynamics, 6th ed., McGraw-Hill, New York, 2001.
Enthalpy of gases
The enthalpy of a gas is estimated by estimating the enthalpy of an ideal
gas. The enthalpy of an ideal gas is calculated using the following equation:
H =H
0
T
0
25
R
+
M
298.15
CP
dT
R
(2.61)
where
H T0 = ideal gas enthalpy of formation at temperature T, kJ/kg
0
H 25
= ideal gas enthalpy of formation at 25C, kJ/kg
R = gas constant, kJ/(kmolK)
M = molecular weight
CP = isobaric specific heat, kJ/(kgC)
T = temperature, K
The ideal gas enthalpy of formation at 25C is presented in Table 2.8 [4].
The enthalpy of a real gas is estimated by using the following equation [1]:
HT = H T0 + H R
(2.62)
Chapter two:
Thermodynamics
31
MW
Heat of formation
at 25C (kJ/kg)
Methane
16.043
4645.1
Ethane
30.070
2787.5
Propane
44.097
2373.9
n-Butane
58.123
2164.2
i-Butane
58.123
2308.5
n-Pentane
72.150
2034.1
n-Hexane
86.177
1937.2
n-Heptane
100.204
1872.7
n-Octane
114.321
1827.4
where
HT = enthalpy of real gas, kJ/kg
HR = residual enthalpy, kJ/kg
Residual enthalpy is calculated as [1]
d ln (Tr )
HR
1
=
1 qI
Z 1 +
RT
M
d ln(Tr )
(2.63)
Different equations are used for different EOSs to calculate the value
of (Tr) are indicated below [1].
For the PR EOS
(Tr ) = [1 + (0.37464 + 1.54226 0.26992 2 )(1 Tr0.5 )]2
(2.64a)
(2.64b)
32
0.457235(Tr )
0.077796Tr
(2.65a)
q=
0.42747 (Tr )
0.08664(Tr )
(2.65b)
(2.66)
Pr
Tr
(2.67a)
Pr
Tr
(2.67b)
where
Z = compressibility
and for the PR EOS
= 0.077796
For the SRK EOS
= 0.08664
where
Pr = reduced pressure
Tr = reduced temperature
Tpc =
xT
i ci
i =1
(2.68)
Chapter two:
Thermodynamics
33
x P
Ppc =
i ci
(2.69)
i =1
x
i
(2.70)
i =1
wi
H i0
where
Tpc = pseudocritical temperature of the mixture, K
Tci = critical temperature of component i, K
xi = mole fraction of component i
Ppc = pseudocritical pressure of the mixture, kPa
Pci = critical pressure of component i, kPa
= mixture acentric factor
i = acentric factor of component i
H0 = ideal gas enthalpy of the mixture, kJ/kg
xwi = weight fraction of component i
H i0 = ideal gas enthalpy of component i
n = number of components
Example 2.7
Estimate the enthalpy of methane at 293.15 K and 10,101.3 kPa and
n-butane at 500 K and 5000 kPa. Use the PR EOS for the calculation.
SOLUTION
Enthalpy of methane
The enthalpy of methane at 25C is 4645.1 kJ/kg.
The change in enthalpy for a temperature change from 298.15 to
293.15 K is calculated using the following equation:
T2
dH =
C dT
P
T1
R
T12 2
T13 3
(k 1)
AT1 (k 1) + B (k 1) + C
M
2
3
(2.71)
34
where
R = gas constant, kJ/(kmolK) = 8.314
T1 = initial temperature = 298.15
k = temperature ratio = 0.983
A = constant = 1.702
B = constant = 9.081 * 103
C = constant = 2.164 * 106
M = molecular weight = 16.043
Differential enthalpy = 10.9 kJ/kg
The enthalpy of ideal methane at 20C is 4656 kJ/kg
Calculation of residual enthalpy
The compressibility of methane at 10,101.3 kPa and 293.5 K is 0.8179.
(The calculation of compressibility has been discussed before.)
Acentric factor = 0.011498
Critical pressure = 4640.7 kPa
Critical temperature = 190.7 K
Reduced pressure = 2.177
Reduced temperature = 1.573
Value of (Tr) = 0.82065
Value of q = 3.1376
Value of I = 0.1263
Residual enthalpy = 120.2 kJ/kg
Enthalpy of real gas = 4776.2 kJ/kg
(HYSYS calculated enthalpy = 4795 kJ/kg)
Enthalpy of n-butane
The enthalpy of methane at 25C is 2164.2 kJ/kg.
The change in enthalpy for a temperature change from 298.15 to
500 K is calculated using the following equation:
T2
dH =
C dT
P
T1
R
T12 2
T13 3
(k 1)
AT1 (k 1) + B (k 1) + C
M
2
3
where
R = gas constant, kJ/(kmolK) = 8.314
T1 = initial temperature = 298.15
k = temperature ratio = 1.6773
A = constant = 1.935
B = constant = 36.915*103
C = constant = 11.402*106
M = molecular weight = 58.123
Chapter two:
Thermodynamics
35
(2.72)
where
0
S25
= entropy of ideal gas at 25C, kJ/(kgK)
B,C,D,E,F,G = constants
The constants used in the above equation are presented in Table 2.9.
The ideal gas entropy at temperature T can be calculated using the
following equation [4]:
T
0
ST0 = S25
+
298.15
C P0
dT
T
(2.73)
or
T
R
CT 2 DT 2
S =S +
A ln T + BT +
M
2
2 298.15
0
T
0
25
(2.74)
36
Methane
0.53829 0.21141
0.33928 1.16432
1.38961 0.50287
Ethane
0.26461 0.02457
0.29140 1.28103
1.81348
0.08335
Propane
0.16030
0.12608
0.18143 0.91891
1.35485
0.26090
n-Butane
0.09969
0.26655
0.05407 0.42927
0.66958
0.34597
i-Butane
0.09907
0.23874
0.09159 0.59405
0.90965
0.30764
n-Pentane
0.11183
0.22852
0.08633 0.54465
0.81845
0.18319
n-Hexane
0.08971
0.26535
0.05778 0.45221
0.70260
0.21241
n-Heptane
0.08978
0.26092
0.06345 0.48471
0.75546
0.15776
n-Octane
0.07780
0.27936
0.05203 0.46312
0.75074
0.17417
Nitrogen
0.25410 0.01662
0.01530 0.03100
0.01517
0.04868
Oxygen
0.22172 0.02052
0.03064 0.10861
0.13061
0.14841
Hydrogen
3.19962
Hydrogen sulfide
0.23745 0.02323
0.03881 0.11329
0.11484 0.04064
Carbon monoxide
0.25284 0.01540
0.01608 0.03434
0.01757
0.10562
Carbon dioxide
0.15884 0.03371
0.14811 0.96620
2.07383
0.15115
0.39279 0.29345
Source: Adapted from Smith, J.M., Van Ness, H.C., and Abbott, M.M., Introduction to Chemical
Engineering Thermodynamics, 6th ed., McGraw-Hill, New York, 2001.
Note: Values for other components are available in the literature [4].
where
ST0 = entropy of ideal gas at temperature T, kJ/(kgK)
0
S25
= entropy of ideal gas at 25C, kJ/(kgK)
C P0 = specific heat of ideal gas, kJ/(kgK)
T = temperature, K
A,B,C,D = constants as per Table 2.4
R S0 S
M R
where
S = entropy of real gas, kJ/(kgK)
ST0 = entropy of ideal gas at temperature T, kJ/(kgK)
(2.75)
Chapter two:
Thermodynamics
37
(2.76)
where
HR = residual enthalpy, kJ/kg; calculated using the previous method
f/p = fugacity correction
p = pressure, kPa
T = temperature, K
Tc = critical temperature, K
M = molecular weight
Fugacity correction
Fugacity correction can be calculated using the following equation [4]:
0
f
f
ln = ln +
h
p p
f h f 0
ln ln
p
p
(2.77)
f
B
C
D
ln p = Z 1 ln Z + V + 2V 2 + 5V 5 + E
r
r
r
(2.78)
where
Z = compressibility
Other parameters are calculated using the method described under
specific heat calculation and constants in Table 2.5.
38
S =
0
x
i =1
0
wi i
( xi ln xi )
M
where
S0 = entropy of the gas mixture, kJ/(kgK)
xwi = weight fraction of component i
R = gas constant, kJ/(kmolK)
M = molecular of the gas mixture = i xi Mi
xi = mole fraction of component i
Mi = molecular weight of component i
Example 2.8
Estimate the entropy of the following pure components using the
PR EOS.
a. Methane at 10,000 kPag and 20C
b. Ethane at 4800 kPag and 30C
SOLUTION
a. Methane at 10,000 kPag and 20C
Phase = vapor
Entropy at 25C = 11.629 kJ/(kgK)
Entropy at 20C = 11.593 kJ/(kgK)
Residual enthalpy calculated using the previous method =
120.2 kJ/kg
Entropy pressure correction = 6.27
8.314
Entropy at 10,000 kPag, 20C = 11.593
* 6.27
16.04
= 8.343kJ/(kgK)
(HYSYS calculated value is 8.733 kJ/(kgK))
b. Ethane at 4800 kPag and 30C
Phase = liquid
Entropy at 25C = 7.626 kJ/(kgK)
Entropy at 30C = 7.656 kJ/(kgK)
Residual enthalpy calculated using the previous method =
300.8 kJ/kg
Entropy pressure correction = 9.803
(2.79)
Chapter two:
Thermodynamics
39
8.314
* 9.803
30.07
= 4.945 kJ/(kgK )
(HYSYS calculated value is 4.664 kJ/(kgK))
1 1
= exp A *
T B
(2.80)
Methane
Ethane
Propane
n-Butane
i-Butane
n-Pentane
n-Hexane
n-Heptane
n-Octane
Nitrogen
Oxygen
Hydrogen
Hydrogen sulfide
Carbon monoxide
Carbon dioxide
Methanol
Ethanol
Propanol
Benzene
Toluene
Water
114.14
156.60
222.67
265.84
302.51
313.66
362.79
436.73
473.70
90.3
85.68
13.82
342.79
94.06
578.08
555.30
686.64
951.04
545.64
467.33
658.25
57.60
95.57
133.41
160.20
170.20
182.48
207.09
232.53
251.71
46.14
51.50
5.39
165.54
48.90
185.24
260.64
300.88
327.83
265.34
255.24
283.16
40
where
= viscosity, cP
A,B = constants as per Table 2.10
T = temperature, K
Viscosity of water
The viscosity of water at low pressure can also be calculated using the
following equation. The following equation is valid for a temperature
range of 0150C.
609.246
= exp 3.827 +
138.89 + t
(2.81)
where
= viscosity, cP
t = temperature, C
1000 ATRB
(1 + (C/TR ) + (D/TR2 ))
(2.82)
where
= viscosity, cP
TR = temperature, R
A,B,C,D = constants as per Table 2.11
m =
x
i
i =1
where
m = viscosity of the mixture, cP
i = viscosity of component i, cP
n = number of components
xi = mole fraction of component i
1/3
i
(2.83)
Chapter two:
Thermodynamics
41
Methane
Ethane
Propane
n-Butane
i-Butane
n-Pentane
n-Hexane
n-Heptane
n-Octane
Nitrogen
Oxygen
Hydrogen
Hydrogen sulfide
Carbon monoxide
Carbon dioxide
Water
3.715E7
1.737E7
1.670E7
1.528E7
5.090E7
3.853E8
1.155E7
4.100E8
1.806E8
4.588E7
7.906E7
1.201E7
3.223E8
8.133E7
1.639E6
4.152E7
5.901E1
6.799E1
6.861E1
6.944E1
5.214E1
8.476E1
7.074E1
8.284E1
9.292E1
6.081E1
5.634E1
6.850E1
1.017
5.338E1
4.600E1
6.778E1
190.3
178.0
322.7
409.9
412.2
75.10
282.8
154.4
99.16
98.48
173.3
1.06
670.3
170.5
522.0
1525.0
0
0
2.67E4
4.73E4
0
0
0
0
0
0
0
4.536E2
2.08E5
0
0
2.4E5
Source: Adapted from Technical Data BookPetroleum Refining, 4th ed., American Petroleum
Institute, Washington, D.C., 1982.
Note: Values for other components are available in the literature [4].
m =
i =1
i
n
1+
j =1
ji
ij =
ij
xj
xi
where
m = viscosity of the mixture, cP
i = viscosity of component i, cP
ij = interaction parameter of component i with respect to j
xi = mole fraction of component i
xj = mole fraction of component j
Mi = molecular weight of component i
Mj = molecular weight of component j
n = number of components in the mixture
(2.84)
(2.85)
42
Example 2.9
Mole fraction
Methane
Ethane
Carbon monoxide
Carbon dioxide
Nitrogen
0.9
0.02
0.02
0.03
0.03
SOLUTION
The viscosity of individual components can be calculated as
Constants
B
Component
Methane
Ethane
Carbon monoxide
Carbon dioxide
Nitrogen
3.715E7
1.737E7
8.133E7
1.639E6
4.588E7
0.5901
0.6799
0.5338
0.4600
0.6081
Viscosity (cP)
190.3
178.0
170.5
522.0
98.48
0
0
0
0
0
0.0114
0.0095
0.0179
0.0152
0.0179
Mi
Mj
ij
ij (xj/xi)
16.043
16.043
16.043
16.043
30.070
30.070
30.070
30.070
28.010
28.010
28.010
28.010
44.010
44.010
44.010
44.010
28.014
28.014
28.014
28.014
30.070
28.010
44.010
28.014
16.043
28.010
44.010
28.014
16.043
30.070
44.010
28.014
16.043
30.070
28.010
28.014
16.043
30.070
28.010
44.010
1.4824
1.0340
1.3500
1.0332
0.6623
0.7228
0.9526
0.7223
0.9344
1.4619
1.3561
0.9992
0.6592
1.0411
0.7328
0.7322
0.9352
1.4633
1.0008
1.3573
0.03294
0.02298
0.04500
0.03444
29.80284
0.72275
1.42885
1.08341
42.04872
1.46190
2.03408
1.49880
19.77659
0.69409
0.48850
0.73224
28.05564
0.97552
0.66720
1.35726
ij (xj/xi)
0.13536
33.03785
47.04350
21.69142
31.05562
Chapter two:
Thermodynamics
43
(2.86)
i j ij
1
1
k ij = 2 +
ki k j
(2.87)
Freezing
Methane
Propane
n-Butane
n-Pentane
n-Hexane
n-Heptane
n-Octane
Benzene
Toluene
o-Xylene
m-Xylene
p-Xylene
182.5
187.7
138.3
129.7
95.3
90.6
56.8
5.5
95.0
25.2
47.9
13.3
Normal boiling
161.5
42.0
0.5
36.1
68.7
98.4
125.7
80.1
110.6
144.4
139.1
138.4
At normal boiling
temperature
0.2246
0.2130
0.1869
0.1782
0.1622
0.1598
0.1519
0.1493
0.1615
0.1430
0.1475
0.1326
0.1883
0.1289
0.1176
0.1086
0.1042
0.1025
0.0981
0.1265
0.1116
0.1040
0.1035
0.1031
Source: Adapted from Technical Data BookPetroleum Refining, 4th ed., American Petroleum
Institute, Washington, D.C., 1982.
Note: Values for other components are available in the literature [4].
44
i =
xiVi
x V
j
(2.88)
= 1
(2.89)
where
km = thermal conductivity of the mixture, W/(m.K)
i, j = volume fraction of pure components i and j
ki, kj = thermal conductivity of pure components i and j, W/(m.K)
Vi, Vj = molar volume of pure components i and j, m3 per kgmol
xi, xj = mole fraction of pure components i and j
Example 2.10
Calculate the thermal conductivity of the following liquid mixture at
0 kPag and 30C.
n-Pentane = 40 vol%
n-Hexane = 30 vol%
n-Heptane = 30 vol%
The following data are available for the calculation:
Component
n-Pentane
n-Hexane
n-Heptane
Density (kg/m3)
MW
615.6
652.4
673.8
72.15
86.18
100.2
0.1172
0.1321
0.1487
SOLUTION
Thermal conductivity of n-pentane at 30C = 0.1112 W/(m.K)
Thermal conductivity of n-hexane at 30C = 0.1179 W/(m.K)
Thermal conductivity of n-heptane at 30C = 0.1232 W/(m.K)
k11 = k1 = 0.1112
k 22 = k 2 = 0.1179
k 33 = k 3 = 0.1232
k12 = k 21 = 0.1145
k13 = k 31 = 0.1169
k 23 = k 32 = 0.1205
1 = 0.4, 2 = 0.3, 3 = 0.3
Thermal conductivity of the liquid mixture = 0.1167 W/(m.K)
Chapter two:
Thermodynamics
45
A 103
B 105
C 108
Methane
Ethane
Propane
n-Butane
n-Pentane
n-Hexane
n-Heptane
n-Octane
16.77
8.74
7.54
6.91
6.76
6.42
4.95
3.59
4.358
4.343
3.362
2.809
2.337
2.214
2.444
2.710
1.335
1.364
1.971
2.841
2.778
2.180
1.685
1.175
Source: Adapted from Technical Data BookPetroleum Refining, 4th ed., American
Petroleum Institute, Washington, D.C., 1982.
Note: Values for other components are available in the literature [4].
(2.90)
where
k = thermal conductivity, Btu/(h.ft.F)
A,B,C = constants (refer to Table 2.13)
T = temperature, F
The thermal conductivity of pure hydrocarbon vapor mixtures can be
calculated as [4]
n
km =
1
i =1
yi
ki
n
A y
ij
(2.91)
j
j =1
where
km = thermal conductivity of the mixture, Btu/(h.ft.F)
ki = thermal conductivity of component i, Btu/(h.ft.F)
n = number of components in the mixture
yi, yj = mole fraction of components i and j
1
Aij = 1 +
4
i M j 0.75 (1 + (Si /T ))
j Mi (1 + (Sj /T ))
0.5 2
(1 + (Sij /T ))
1 + (Si /T )
(2.92)
46
Si, Sj = 1.5 Tb
Sij = SiSj
i, j = viscosities of components i and j, cP
Mi, Mj = molecular weight of component i and j
Tb = normal boiling point, R
T = temperature, R
Flash calculation
Flash calculation is probably the most important unit operation to solve
process engineering problems. Any mixture at a defined pressure and
temperature can exist either in a liquid phase or in a vapor phase, or in
two phases. Flash calculation is required to establish the state of the fluid
under a specific condition.
Vaporliquid equilibrium
When a fluid exists in two phases, the mole fraction of any component in
the vapor and liquid phases differs depending on the vaporliquid equilibrium constant. The higher the value of the vaporliquid equilibrium,
the higher will be the ratio of mole fraction between the vapor and liquid
phases. Mathematically
Ki =
yi
xi
(2.93)
where
Ki = vaporliquid equilibrium constant of component i
yi = mole fraction of component i in vapor phase
xi = mole fraction of component i in liquid phase
Once the value of the equilibrium constant is known, it is easy to do
a flash calculation and the bubble and dew points can be calculated using
the following equations:
Bubble point
y = K x
= 1.0
(2.94)
x = K
= 1.0
(2.95)
i i
Dew point
yi
Chapter two:
Thermodynamics
47
It is clear from the above analysis that a flash calculation can proceed
only when an accurate equilibrium constant is available. Any flash calculation is initiated with the preliminary estimated values for equilibrium
constants. A large number of correlations and graphs are available in the
literature and a preliminary estimate can be made using the following
equation [9]:
Ki =
Pci
T
exp 5.37(1 + i ) 1 ci
P
T
(2.96)
where
Ki = vaporliquid equilibrium constant of component i
Pci = critical pressure of component i
Tci = critical temperature of component i
i = acentric factor of component i
P = operating pressure
T = operating temperature
The mole fraction of component i in the liquid and vapor phases can
be estimated as [9]
xi =
zi
1 + V (K i 1)
(2.97)
yi = x i K i
(2.98)
zi (K i 1)
1 + V(K 1) = 0
i =1
(2.99)
where
zi = overall mole fraction of component i
V = vapor phase mole fraction
Other terms are as defined before.
Using the above equations, the compositions in the vapor and liquid phases can be calculated using a set of equilibrium constants. The
adequacy of the calculation needs to be checked through the calculation
of the fugacity of each component. For the correct equilibrium condition,
the fugacity of each component in both the vapor and liquid phases will
be the same. If the fugacity is different, the equilibrium constants are
48
x a
2
fk
bk
A
ln
=
(Z 1) ln (Z B)
xk P
b
2 2B
Z + 2.414B
ln
Z 0.414B
i ik
bk
b
(2.100)
where
a=
x x a
(2.101)
x b
(2.102)
b=
j ij
i i
aij = (1 ij ) ai0.5 a 0j .5
(2.103)
Programming
Calculation of JT effect due to drop in pressure
This program has been developed to estimate the impact of the Joule
Thomson effect when a gas is expanded through a pressure reduction
unit. The following basis has been used in this estimation:
The calculation is based on the PR EOS.
It is assumed that the expansion is adiabatic and not isentropic.
Generally, the temperature drop is larger in isentropic expansion in
comparison to adiabatic expansion.
This calculation assumes only the vapor phase expansion and does
not perform any enthalpy balance due to a change in phase.
Chapter two:
Thermodynamics
49
Nomenclature
a
CP
CV
EK
EP
F
gc
H
l
K
m
MW
acceleration, m/s2
heat capacity at constant pressure, kJ/(kgC)
heat capacity at constant volume, kJ/(kgC)
kinetic energy
potential energy
force, N
acceleration due to gravity, m/s2
enthalpy, kJ
displacement, m
vaporliquid equilibrium constant
mass, kg
molecular weight
50
P
Q
R
S
T
U
v
V
W
z
Z
pressure, kPa
heat, kJ
universal gas constant, kJ/(kmolK)
entropy, kJ/(kmolK)
temperature, K
internal energy, kJ
velocity, m/s
volume, m3
work, kNm
elevation, m
compressibility
Greek characters
References
1. Smith, J.M., Van Ness, H.C., and Abbott, M.M., Introduction to Chemical
Engineering Thermodynamics, 6th ed., McGraw-Hill, New York, 2001.
2. Peng, D.Y. and Robinson, D.B., A two constant equation of state, I.E.C.
Fundamentals, 15, 5964, 1976.
3. Soave, G., Equilibrium constants from a modified Redlich-Kwong equation
of state, Chemical Engineering Science, 27(6), 1197, 1972.
4. Technical Data BookPetroleum Refining, 4th ed., American Petroleum
Institute, Washington, D.C., 1982.
5. Coulson, J.M. and Richardson, J.F., Chemical Engineering, Volume 6 (SI Unit),
Pergamon Press, USA, 1986.
6. Perry, R.H. and Green, D., Perrys Chemical Engineering Handbook, 6th ed.,
McGraw-Hill, Malaysia, 1984.
7. Moran, M.J. and Shapiro, H.N., Fundamentals of Engineering Thermodynamics,
5th ed., John Wiley, USA, 2004.
8. Bromley, A. and Wilke, C.R., Viscosity behavior of gases, Industrial and
Engineering Chemistry Chemical Engineering Science, 43(7), 1641, 1951.
9. Naji, H.S., Conventional and rapid flash calculations for the Soave-RedlichKwong and Peng-Robinson equations of state, Emirates Journal for Engineering
Research, 13(3), 8191, 2008.