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Chapter 1
Pure Component Properties Using EOS
1.1 Compressibility Factors Using PR-EOS
The gas cylinders distributed by Jordan Petroleum Re nery Company (JPRC) contain
a mixture of propane and n-butane. Assume they contain only n-butane. The volume
of the cylinder is about 30 liters and the net mass of its contents is 15 kg. In winter,
the temperature of the cylinder can be assumed to be 15 C, and the pressure inside the
cylinder is 12 bars.
1. Use the Peng-Robinson equation of state to determine what are the phase(s) inside the
cylinder.
2. Repeat the same calculations as in the rst part if the pressure is reduced to 7 bars.
What are the mass fraction of the liquid and that of the vapor?
The following general solution procedure for the use of EOS in compressibility
calculations is recommended to be followed:
1. Obtain the properties of the component of interest from any reference you deem
useful. I am using the properties package coming with Sandler's book.
Component M W (g/mol) Tc (K) Pc (MPa) ! (-)
.
n-butane
58.124
425.2
3.80 0.199
2. Determine the covolume (b) and energy (a) parameters from the proper EOS. This
time the PR-EOS is used,
RTC
b = 0:07780
;
(1)
PC
= 0:37464 + 1:5422! 0:26992! 2
(2)
(
"
#)2
1=2
T
(T ) =
1+
1
;
(3)
TC
a(T )
0:45724
R2 TC2
(T ):
PC
(4)
3. Determine the reduced covolume (B) and energy (A) parameters. Once the covolume
and the energy parameters are determined, we can make a better utilization of their
values by using their reduced equivalents i.e.,
bP
B =
;
(5)
RT
aP
A =
(6)
(RT )2
Section 1.1
4. Find the coef cients in the compressibility cubic according to the proper EOS. For the
PR-EOS the coef cients of this cubic are given as
0 = Z 3 + a2 Z 2 + a1 Z + a0
(7)
a2 = B 1;
(8)
2
a1 = A 3B
2B;
(9)
2
3
a0 =
AB + B + B ;
(10)
5. Solve for the roots of the compressibility cubic. Two approaches exists: numerical
and analytical solutions. The solution for these conditions yields only one real root
Z =0.0472. This is equivalent to one single phase which is a subcooled liquid
phase since the total pressure is higher than the vapor pressure of n-butane at this
temperature.
The butane problem at 288.15 K and 12 bar is solved for the compressibility using the
following sequence of steps
Chapter 1
(8:314)(425:2)
= 7:2446 10 5 ;
3:80 106
= 0:37464 + 1:5422(0:199) 0:26992(0:199)2 = 0:6708;
(
"
#)2
1=2
288:15
(T ) =
1 + 0:6708 1
= 1:2513;
425:2
b
a(T )
A =
a2 =
a1 =
a0 =
0 =
0:07780
(8:314)2 (425:2)2
(1:2513) = 1:8837:
3:80 106
(7:2446 10 5 )(12 105 )
= 0:0363;
(8:314)(288:15)
(1:8837)(12 105 )
= 0:3938;
(8:314)2 (288:15)2
0:0363 1 = 0:9637;
0:3938 3(0:0363)2 2(0:0363) = 0:3173;
0:3938(0:0363) + (0:0363)2 + (0:0363)3 =
3
Z
0:9637Z 2 + 0:3173Z 0:0129:
0:45724
0:0129;
Solution with initial guess Z = B To determine the liquid like root, on starts with an
initial guess Z0 = B and carries out the iterations using NR method.
(0:0363)3 0:9637(0:0363)2 + 0:3173(0:0363) 0:0129
Z1 = 0:0363
= 0:04677
3(0:0363)2 + 2( 0:9637)(0:0363) + 0:3173
(0:04677)3 0:9637(0:04677)2 + 0:3173(0:04677) 0:0129
Z2 = 0:04677
= 0:04716
3(0:04677)2 + 2( 0:9637)(0:04677) + 0:3173
(0:04716)3 0:9637(0:04716)2 + 0:3173(0:04716) 0:0129
Z3 = 0:04716
= 0:04716
3(0:04716)2 + 2( 0:9637)(0:04716) + 0:3173
Iterations are repeated until a convergence criteria is reached. Convergence criteria
may be the absolute or relative tolerance in the compressibility and/or function value.
Solution with initial guess Z = 1 To determine the liquid like root, on starts with an
initial guess Z = B and carries out the iterations using NR method.
(1)3 0:9637(1)2 + 0:3173(1) 0:0129
= 0:7549
3(1)2 + 2( 0:9637)(1) + 0:3173
(0:7549)3 0:9637(0:7549)2 + 0:3173(0:7549) 0:0129
Z2 = 0:7549
= 0:5668
3(0:7549)2 + 2( 0:9637)(0:7549) + 0:3173
Iterations are carried out until the convergence criteria is met. This is achieved after 13
iterations as
(0:04716)3 0:9637(0:04716)2 + 0:3173(0:04716) 0:0129
Z13 = 0:04716
= 0:04716:
3(0:04716)2 + 2( 0:9637)(0:04716) + 0:3173
The same root is arrived at as that with the initial guess Z = B. Consequently, we
have only one phase which is a liquid phase.
Z1
Section 1.1
1.1.1.2
The butane problem at 288.15 K and 7 bar is solved for the compressibility using the
following sequence of steps
(8:314)(425:2)
= 7:2446 10 5 ;
3:80 106
= 0:37464 + 1:5422(0:199) 0:26992(0:199)2 = 0:6708;
(
"
#)2
1=2
288:15
(T ) =
1 + 0:6708 1
= 1:2513;
425:2
b
a(T )
A =
a2 =
a1 =
a0 =
0 =
0:07780
(8:314)2 (425:2)2
(1:2513) = 1:8837:
3:80 106
(7:2446 10 5 )(7 105 )
= 0:02117;
(8:314)(288:15)
(1:8837)(7 105 )
= 0:22973;
(8:314)2 (288:15)2
0:02117 1 = 0:97883;
0:22973 3(0:02117)2 2(0:02117) = 0:18605;
0:22973(0:02117) + (0:02117)2 + (0:02117)3 =
Z 3 0:97883Z 2 + 0:18605Z 0:0044052:
0:45724
0:0044052;
Solution with initial guess Z = B To determine the liquid-like root, on starts with an
initial guess Z0 = B and carries out the iterations using NR method.
(0:02117)3 0:97883(0:02117)2 + 0:18605(0:02117) 0:0044052
Z1 = 0:02117
= 0:02731
3(0:02117)2 + 2( 0:97883)(0:02117) + 0:18605
(0:02731)3 0:97883(0:02731)2 + 0:18605(0:02731) 0:0044052
Z2 = 0:02731
= 0:02756
3(0:02731)2 + 2( 0:97883)(0:02731) + 0:18605
(0:02756)3 0:97883(0:02756)2 + 0:18605(0:02756) 0:0044052
Z3 = 0:02756
= 0:02756:
3(0:02756)2 + 2( 0:97883)(0:02756) + 0:18605
Solution with initial guess Z = 1 To determine the vapor-like root, on starts with an
initial guess Z = B and carries out the iterations using NR method.
0:97883(1)2 + 0:18605(1) 0:0044052
= 0:8349
3(1)2 + 2( 0:97883)(1) + 0:18605
(0:8349)3 0:97883(0:8349)2 + 0:18605(0:8349) 0:0044052
Z2 = 0:8349
= 0:7562
3(0:8349)2 + 2( 0:97883)(0:8349) + 0:18605
Iterations are carried out until the convergence criteria is met. This is achieved after 6
iterations as
(0:7333)3 0:97883(0:7333)2 + 0:18605(0:7333) 0:0044052
Z6 = 0:7333
= 0:7333:
3(0:7333)2 + 2( 0:97883)(0:7333) + 0:18605
This is a different root and the same as the root arrived at with the initial guess Z = B.
Z1
(1)3
Chapter 1
2b3
b2
9bc + 27d
54
3c
(14)
q3
(16)
(15)
p
jpj
=
=
=
arccos
1=3
r +q
r
q3
p
p
q3
(17)
b
:
3
(18)
p
2 q cos( =3) b=3
p
2 q cos[( + 2 )=3]
p
2 q cos[( + 4 )=3]
(19)
b=3
b=3:
(20)
(21)
(22)
Solving for the compressibility of butane in the cylinder problem requires the cubic
equation. The coef cients for 288.15 K and 12 bars are available from the PR-EOS as
Discriminator is used loosely since this is not the same as the discriminator for a quadratic equation.
Section 1.1
Z1
1.1.2.2
p
jpj
r2 + q
r
b
=
3
0:01135
j0:01135j
0:28322 + ( 0:002571)
0:2832
( 0:9637)
= 0:04716:
3
The sequence of calculations are the same as the case with one single real root. However,
the discriminator is negative in this case which means we need to calculate the three roots
using equations 19-22. Solving for the compressibility of butane in the cylinder problem
requires the cubic equation. The coef cients for 288.15 K and 7 bars are available from
the PR-EOS as
= Z 3 0:97883Z 2 + 0:18605Z 0:0044052
2( 0:97883)3 9( 0:97883)(0:18605) + 27( 0:0044052)
p =
= 0:006585
54
( 0:97883)2 3(0:18605)
q =
= 0:04444
9
p2 q 3 = ( 0:006585)2 (0:04444)3 = 4: 440 3 10 5
The discriminator in this case is negative. Therefore, we have two phases equivalent to
three real roots which can
! be calculated as:
p
0:006585
= arccos p
= arccos p
= 2:3503
3
0:044443
q
p
0:97883
p
Z1 =
2 q cos( =3) b=3 = 2 0:04444 cos(2:3503=3)
= 0:027562
3
p
0:97883
p
Z2 =
2 q cos[( + 2 )=3] b=3 = 2 0:04444 cos((2:3503 + 2 )=3)
= 0:73331
3
p
0:97883
p
Z3 =
2 q cos[( + 4 )=3] b=3 = 2 0:04444 cos((2:3503 + 4 )=3)
= 0:217 95
3
The maximum root Z = 0:73331 is assigned as the vapor compressibility, while the
minimum root Z = 0:027562 is assigned as the liquid compressibility.
0