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APPENDIX D

COMPRESSIBILITY FACTOR EQUATIONS

D.1 THE REDLICHKWONG EQUATION root of a cubic. Robert C. Reid, John M. Prausnitz, and
Thomas K. Sherwood [The Properties of Gases and
The Redlich-Kwong equation is actually an equation of Liquids, 3rd Ed., McGraw-Hill Book Company, 1977]
state. It was formulated by Otto Redlich and Joseph N. give the cubic as
S. Kwong in 1949 [Chemical Review, 44, 1949, 233-244].
Their equation is z3 z2 + ( A* B*2 B*)z A*B* = 0,

nRT a
P= , where
V b V(V + b) T
a Pr P
a (nR)2 Tc2.5 A* = = 0.42748 5r/ 2 ,
a= , Tr5/ 2
Tr
Pc

b nRTc b Pr P
b= , B* = = 0.086640 r .
Pc Tr Tr

where Tc and Pc are the critical temperature and pres- In the equations below, Pr is the reduced pressure (that
sure of the gas being considered. The constants in the is, the ratio of actual pressure to critical pressure), and
equation are derived as Tr is the reduced temperature (that is, the ratio of actual
temperature to critical temperature). Let A, B, C, D, and
a = [(9)(2)1 / 3 1]1 = 0.42748, E be constants dened by

b = [(2)1 / 3 1]/ 3 = 0.08664. Pr


A = 0.08664 ,
Tr
This equation is quite accurate at the critical tempera-
ture for P/Pc = 4 to 40 (error < 2.5%). At higher tem-
4.9340
peratures and at P/Pc above about 5 the equation B= ,
becomes increasingly inaccurate. Tr3 / 2
The compressibility factor may be found explicitly
from the Redlich-Kwong equation. It is the principal C = A2 + A AB,

Pipe Flow: A Practical and Comprehensive Guide, First Edition. Donald C. Rennels and Hobart M. Hudson.
2012 John Wiley & Sons, Inc. Published 2012 by John Wiley & Sons, Inc.

263
264 COMPRESSIBILITY FACTOR EQUATIONS

TABLE D.1. LeeKesler Constants


Constant Simple Reference Constant Simple Reference
B1 0.1181193 0.2026579 c3 0.0 0.016901
B2 0.265728 0.331511 c4 0.042724 0.041577
B3 0.154790 0.027655 d1 104 0.155488 0.48736
B4 0.030323 0.203488 d2 104 0.623689 0.0740366
c1 0.0236744 0.0313385 0.65392 1.226
c2 0.0186984 0.0503618 0.060167 0.03754

C 1 where
D= ,
3 9 b2 b3 b4
B = b1 ,
Tr Tr2 Tr3
C A2 B 1
E= + + .
6 2 27 c2 c3
C = c1 + ,
Tr Tr3
If D3 + E2 0, then
d2
1 D = d1 + ,
3
z= E+ D +E + E D +E + .
3 2 3 3 2 Tr
3
Pc V( 0 )
Vr( 0 ) = ,
If D3 + E2 < 0, then RTc

1 E 1 and
z = 2 D cos cos1 + .
3 D3 3 (0) 2
exp ( 0 ) 2 = e /( Vr ) .
(Vr )
Critical constants for selected gases are given in Table
D.3 in Section D.3. Chemical Engineers Handbook (5th The constants for these equations for a simple uid are
Ed., McGraw Hill, 1973) indicates that the Redlich- given in Table D.1. (The and shown are for the Lee
Kwong equation of state ts the data for helium and Kesler equation and should not be confused with those
hydrogen only for reduced temperatures of 2.5 and in the Nomenclature.) The equation is solved for Vr( 0 ) ,
higher when their critical temperatures are increased by the ideal reduced volume for a simple uid, and then
8C, and their critical pressures are increased by 8 the simple uid compressibility factor is calculated:
atmospheres.
Pr Vr( 0 )
z( 0 ) = . (D.2)
Tr
D.2 THE LEEKESLER EQUATION
Next, using the same reduced pressure and temperature,
the equation is solved again for Vr( 0 ), but using the refer-
Another equation of state that is much more accurate
ence uid constants from the table; therefore, call this
than the RedlichKwong equation is the LeeKesler
value Vr( R ). Then:
equation. This is a generalized BenedictWebbRubin
equation developed by B.I. Lee and M.G. Kesler in 1975 Pr Vr( R )
from which the compressibility factor may be found. z( R ) = .
Tr
The solution is formidable, but with a computer it can
be obtained without much difculty using the Newton The compressibility factor z for the uid of interest is
Raphson trial-and-error solution technique. Their equa- then calculated from the following formula:
tion is:
z = z( 0 ) + R ( z( R ) z( 0 ) ) ,
Pr V (0)
B C D
r
= 1+ + (0) 2 + (0) 5 +
Tr (0)
Vr (Vr ) (Vr ) where is Pitzers acentric factor, and for the reference
(D.1)
c4 gas, R = 0.3978. The denition of the acentric factor is:
Tr3 (Vr( 0 ) )2 + (V( 0 ) )2 exp (V( 0 ) )2 , = log 10 ( Pvapr )Tr =0.7 1.000,
r r
THE LEEKESLER EQUATION 265

where the pressure term is the reduced vapor pressure c


at Tr = 0.7. (Values of are given for selected gases in f7 = 2 3 4 ( 0 ) 5 ( 0 ) 2 2 exp ( 0 ) 2 .
r r
T (V ) r
(V ) (Vr )
Table D.2 in Section D.3.)
(D.9)
In order to solve the LeeKesler equation by the
NewtonRaphson method, we must devise a function The derivative of the function f (Vr( 0 ) ) is then the sum
from it whose value is zero. This may be done by moving of the derivatives of its terms, or
the PrV(0)/Tr term to the right side of Equation D.1:
f (Vr( 0 ) ) = f2 + f3 + f4 + f5 + f6 + f7. (D.10)
(0)
Pr V B C D
0 = 1 r
+ + + + The solution technique for the f (Vr( 0 ) ) equation is to
Tr Vr( 0 ) (Vr( 0 ) )2 (Vr( 0 ) )5
guess an initial Vr( 0 ) call it (Vr( 0 ) )i =1 . An initial guess for
c4 c Vr( 0 ) may be obtained by nding the RedlichKwong
3 (0) 2
exp ( 0 ) 2 + 3 4 ( 0 ) 4 exp ( 0 ) 2 .
T (Vr )
r (Vr ) Tr (Vr ) (Vr ) compressibility factor zRK and assuming that it is
approximately equal to the simple uid compressibility
Call this function f (Vr( 0 ) ) by substituting f (Vr( 0 ) ) for factor. Then the z(0) equation (Eq. D.2) may be solved
the zero: for (Vr( 0 ) )i =1:

zRKTr
Pr Vr( 0 ) B C (Vr( 0 ) )i=1 . (D.11)
f (Vr( 0 ) ) = 1 + (0) + (0) 2 + Pr
Tr Vr (Vr )
D c This guess for (Vr( 0 ) )i =1 is then inserted into the function
+ 3 4 ( 0 ) 2 exp ( 0 ) 2 + (D.3)
(0) 5
(Vr ) Tr (Vr ) (Vr ) (Eq. D.3) and into the equations for the terms of its
derivative (Eqs. D.4D.11).
c4
exp ( 0 ) 2 . These three values ([Vr( 0 ) ]i =1 , f [Vr( 0 ) ]i =1, and f [Vr( 0 ) ]i =1)
Tr3 (Vr( 0 ) )4 (Vr ) are then used to nd (Vr( 0 ) )i =2 . By dividing the value of the
function (which is the required correction to the function,
f (Vr( 0 ) ) is supposed to equal zero. Of course, it is not that is, to the dependent variable), we transform it into an
likely to equal zero if we dont know the correct value estimate of the required correction in the independent
for ( Vr( 0 )) but have to guess it instead. Any nonzero variable, Vr( 0 ). Equation D.12 applies the correction. The
value for f (Vr( 0 ) ) is the error incurred by using an incor- result is a much closer value of the independent variable,
rect value for ( Vr( 0 ) ) in it. It may be considered to be the as shown in Figure D.1:
required correction for the function. Using the Newton
Raphson method, we can rene our guesses very easily. f (Vr( 0 ) )i
In order to do this we need the derivative of the func- (Vr( 0 ) )i +1 = (Vr( 0 ) )i . (D.12)
f (Vr( 0 ) )i
tion f (Vr( 0 ) ) . The derivatives of the seven terms of the
function are given below: The procedure is then repeated with this better estimate
of (Vr( 0 ) ). After each repetition the correction term
f1 = 0, f (Vr( 0 ) )n / f (Vr( 0 ) )n will become smaller and smaller,
Pr (D.4)
f2 = ,
Tr

B Function: f(Vr(0) )versus Vr(0)


f3 = (0) 2
, (D.5)
(V r )
Result of (Vr(0) )i =1
Guess
f(Vr(0) )

C
f4 = 2 , (D.6) Tangent
(Vr( 0 ) )3 to Curve

D
f5 = 5 , (D.7) 0
Desired
(Vr( 0 ) )6 f(Vr(0) ) Guessed
Improved (Vr(0) )i =1
(0)
c Guess (Vr )i =2
f6 = 2 3 4 ( 0 ) 3 ( 0 ) 2 1 exp ( 0 ) 2 ,
Tr (Vr ) (Vr ) (Vr ) V (0)
(D.8) FIGURE D.1. Solution technique for Vr( 0 ).
266 COMPRESSIBILITY FACTOR EQUATIONS

until it becomes small enoughas small a value as acentric factor may be necessary to achieve the best
desired or allowed by the computational precision of agreement.
the computerthat the solution may be considered to
have been found.
The solution technique described above has one D.3 IMPORTANT CONSTANTS FOR
caveatit works well except in the region of the critical SELECTED GASES
point. There the derivative approaches zero and the
procedure usually gets caught in a loop. To circumvent Following are two tables of important constants neces-
this a different technique must be substituted on the sary to implement the RedlichKwong and LeeKesler
rst occurrence of a change in sign of the correction compressibility factor equations. Table D.2 gives the
term f (Vr( 0 ) ) / f (Vr( 0 ) ). One method is to interpolate acentric factor for selected gases.
between the Vr( 0 ) that caused the sign of f (Vr( 0 ) ) to Table D.3 gives critical constants for the same gases.
change and the one just previous to it to estimate the Data are included for ammonia, hydrogen, and helium
Vr( 0 ) where the curve crosses the f (Vr( 0 ) ) = 0 line. for use in these equations; the data for these gases
The reader will note that Pitzers acentric factor is should be amended as described in Section D.1 for
used in the solution for the compressibility factor z. best results in the RedlichKwong equation, and as
Reid et al. (The Properties of Gases and Liquids, 3rd ed., described above in Section D.2 for best results in the
McGraw-Hill Book Company, New York, 1977) state LeeKesler equation.
that application of correlations employing the acentric Table D.3 includes critical constants from various
factor should be limited to normal uids; in no case authorities. It is suggested that consensus values or aver-
should such correlations be used for H2, He, Ne, or for ages of all the values be used for each constant.
strongly polar and/or hydrogen-bonded uids. There-
fore, for these nonnormal uids it is suggested that the
TABLE D.2. Acentric Factor for Selected Gases
compressibility factor yielded by the LeeKesler equa-
tion be compared with actual uid data compressibility Acetylene 0.184 CO2 0.225 Methane 0.008
factors on a plot such as Figure 1.3 in Chapter 1. From Air 0.036 Helium 0.387 Nitrogen 0.040
this plot it may be seen what shift in critical constants Ammonia 0.250 n-Hydrogen 0.22 Oxygen 0.021
will bring the LeeKesler compressibility factor into Argon 0.004 p-Hydrogen 0.219 Propane 0.152
congruence with the real compressibility factor for the See Table D.3 footnote d for bibliography. Parahydrogen is calcu-
largest region on the chart. Several modications of the lated from footnote g data.
IMPORTANT CONSTANTS FOR SELECTED GASES 267

TABLE D.3. Critical Constants for Selected Gases According to Various Authorities
Handbook of National
Marks Perry and Poling Chemistry ASME Fluid Bureau of
Gas Parameter Handbooka Chiltonb Ranjevic et al.d and Physicse Metersf Standardsg
Acetylene Tc R 556.0 556.5 555.93 554.94 554.9 557.1
Pc psia 911 911 920 886.8 890.2 905
Air Tc R 239.4 238.4 238.41 238.4
Pc psia 547 547 546 547
Ammonia Tc R 730 730.0 729.99 729.72 729.9 731.1
Pc psia 1639 1639 1639 1646.6 1646 1657
Argon Tc R 272.0 272 271.35 271.55 271.56 272.08 272.0
Pc psia 705 705 705 710.4 710.4 705.4 711.5
CO2 Tc R 547.7 547.7 547.47 547.42 547.43 547.7
Pc psia 1073 1073 1067 1070 1070.00 1073
Helium Tc R 9.5 9.5 9.45 9.34 9.34 9.4 9.363
Pc psia 33.2 33.2 33.1 32.9 32.9 33.0 32.99
n-Hydrogen Tc R 59.9 59.9 59.85 59.85 59.35 59.9
Pc psia 188 188 187 188.1 187.5 188
p-Hydrogen Tc R 59.29
Pc psia 186.2
Methane Tc R 343.2 343.2 343.17 343.01 343.01 343.2 343.00
Pc psia 673 673 671 667.0 667.0 673.1 666.9
Nitrogen Tc R 226.9 226.9 226.89 227.16 227.18 226.9 227.27
Pc psia 492 492 492 492.8 492 492 493.0
Oxygen Tc R 277.9 277.8 277.83 278.24 278.26 277.9 278.25
Pc psia 730 730 731 731.4 731.4 730 731.4
Propane Tc R 665.93 665.9 665.91 665.69 665.69 666 665.73
Pc psia 617.4 617 616 616.1 616.1 617.4 616.1
a
Baumeister, T., E. A. Avallone, and T. Baumeister III, eds., Marks Standard Handbook for Mechanical Engineers, 8th ed., McGraw-Hill, 1978.
b
Perry, R. H. and C. H. Chilton, Chemical Engineers Handbook, 5th ed., McGraw Hill, 1973.
c
Ranjevi, K., Handbook of Thermodynamic Tables and Charts, Hemisphere Publishing Corporation, 1976.
d
Poling, B. E., J. M. Prausnitz, and J. P. OConnel, The Properties of Gases and Liquids, 5th ed., McGraw-Hill, 2001.
e
Lide, D. R., ed., CRC Handbook of Chemistry and Physics, 85th ed., CRC Press Inc., 2004.
f
Interim Supplement No. 19.5 on Instruments and Apparatus (Application, Part II of Fluid Meters, 6th ed.), American Society of Mechanical Engi-
neers, 1971.
g
McCarty, R. D., NBS Standard Database 12 (MIPROPS), National Bureau of Standards, 1986.