m

I Sodaty of PotrobumEn@wra I

SPE 26667 A Simple Cubic Equation of State for Hydrocarbons and Other Compounds
Mohsen Mohsen-Nia, U, of Illinois;HamiciMrxidaress,Amir-KabirU,; and (3A, Mansoori,* U. of illinois
SP~ Member E C$fWhl1SS3,
SOMY of Petroloum Englneara, for preaemalien 1.s, This paper wae wcpued m tfw SSlfr Annual T4cfmical ConfSlenCO and Exhlblllon 01 the Soclsly of P9ttOImim Englnoers held In Houslon, Texas, 3--S Octobe? 1993.

Thla papaf wan eekctad fof praaematkm by an SPE Program Commltfee followlng revlow of Information mntalrrad In M abatrac! submitted by the author(s). Contents Of Iho paper, M pfaeamad, havo m baen rovkwed by tM Soahty 01 Palralcum Eriulnaera and NO sutijeal to cor?eaflon by the author(s). The material, m preeemed, does not nacaaaar:: rellect MY* of t~ *fy of P@*um E%ffIsw$, M ~ffk.m. W membam. pepera Pr*MntWf at SPE mawngs are Wbjact to publication ravlsw by Edit. rlal Committals of the Society of Pef@awn Englrrme. Pemtbabn10VWYb reatrkfad teen #mrecf 01 M me than SW wwd:. Illuslrwkms may rwI bo c@led. The sbatracl ahwld centuln consplcuoua acknowledgment of Wwra srid by whom the paper la pfeaemed. Write Llbfarlan, SPE, P,O. Sax S33S3S, Rkhwdaon, 7!( 76CWMS3S, U.fi.A. Telex, 1S3245 SPEUT.

ABSTRACT

INTRODUCTION A new simple two-constant cubic equations of state for hydrocarbons, hydrocarbon mixtures, and other nonassociating compounds is introduced. This equation of state is based on the statistical mechanical information available for the repulsive thermodynamic functions and the phenomenological knowledge of the attractive intermolecular potential tail contributions to the thermodynamic properties. This new two-constantparameter cubic equation is in the following form: The success of oil and gas recovery, production, and processing operations is related to the availability of accurate and simple equations of state for prediction of thermodynamic properties of fiuids. Recent developments in modeling the phase behavior of reservoir fluids indicate that more wwiousconsiderations must be given to fundamental approaches to produce simple and accurate equations of state*-9. Although, there has been considerable progress made in the development of equations of state based on the statistical mechanics, the cubic equations of state are stili wideiy preferred in industrial calculations. Equations such as the van der Waals, Rediich-Kwong, Heyen and their modifications are extensively used in petroleum and naturai gas engineering caiculationsl-. In this report, we first present a simplified, but accurate, equation for the positive (repulsive) term of equations of state. men we introduce a new version of cubic equations of state using the simplified repulsive term deveioped in part L A new cubic equation of state which contains two constant parameters is then introduced. The resulting equation of state is used for property prediction of a variety of hydrocarbons, other fluids, and mixturee of practical interest. This equation of state is shown to be a simple cubic equation with superior accuracy than the RK equation which has been considered to be the most accurate two-constant-parameter cubic equations of state.

and ati =0.48748 R%diw /P@ and ~ii =0.064662RTdi/P~i It is shown that this equation of state is more accurate than the Redlich-Kwong equation, which has been considered to be the best two-constant-parameter cubic equation of state. This new equation is appiied for calculation of thermodynamic properties of hydrocarbons and other non-associating fluids and fiuid mixtures of interest in the oil and gas industries. References and illustrations at the end of paper. 651

-t

~s

A SIMPLE CUBIC EQUATION OF STATE FOR HYDROCARBONS AND OTHER COMPOUNDS

SPE 26667

THE NEW REPULSIVETERM OF EQUATIONS OFSTATE The importance of short-range repulsive forces in an equation of state for determining the thermodynamic properties of fluids is well established by the works of numerous investigators.2bylG.This is because more accurate expression for the repulsive term of an equation of state results in a better agreement with the experimental data. However, the major weakness of the industrial equations of state is due to their inaccurate repulsive term,
z (W) = 1%/RT = v/(v-b)

v~ln appearing in Table 1 is the smallest molar volume for fluids which can be calculated based on different equations of state (approximately the molar volume at the triple-point) when the MCSL repulsive equation of state is used to modify the above equations (replacing v/(v-b) with eq. 2). Of course the MCSL equation of state is valid for v/b values as low as 0.25. Considering the fact that the v/b in the cubic equations of state (excluding the van der Waals equation which, because of its inaccuracy, is not used for practical calculations) do not go below 0.7 we propose Lhe following repulsive equation of state for v/b> 0.2
z ,,p = 1%/RT=
(V +

(1) 0.62b)/(v-O.47b) (5)

An accurate equation for representing the repulsive effect is the MCSL equation which reduces to the following form for pure fluids%
z ~rq)=Pv/RT=

[64v%16vzb+4vb2

-b3]/[4v-b]3

(2)

This equation can replace the repulsive term, v/(v-b), in the cubic equations. However, due to the fact that after this modification the resulting equation of state was not going to be cubic any more Scott4 introduced the following equation for the repulsive term of pure fluid equations of state. z ~w) = Pv/RT=
(V +

This equation reproduces the MCSL equation for the repulsive fluid with good accuracy for v/b >0.7 as it is demonstrated in Figures 1 and 2. In Figure 1 the percentage deviation of calculating the repulsive compressibility factor from the exact MCSL equation as calculated by eq. (5) is compared with the Scott and Kim, et.al models. According to tlis figure eq. (5) is in better agreement with the MCSL equation than the other simplified repulsive equations for v/b >0.7. In Figure 2 the repulsive excess Helmholtz free energy (over the ideal gas) , (A- Aig)/RT= - 2.319Ln(l - 0.47b/v) (6)

0.5b)/(v -0.5 b)

(3)

Similarly, Kim, et al. (1986) presented another equation for repulsive term of equations of statw
z (W) = R/RT

= (V

0.77b)/(v -0.42 b).

(4)

as derived from eq. (5) is compared with the similar calculations using the Scott and Kim, et,al models. According to this figure eq. (6) is in better agreement with the accurate MCSL equation of state than the other simplified repulsive models. We have extended the applicability of equations (5) and (6) to repulsive mixtures by writing them in the following forms
z ~[rql = (v + 0.62bJ/(v

Neither of the above two equations are accurate enough to replace eq.(2)as it is demonstrated in Figure L In order to produce a simple, but accurate, repulsive term for cubic equations of state, we consider a number of representative cubic equations of state in a generalized from as shown in Table 1. m Parameters of a generalized equation of state Z = Pv/RT = Z(q) -(av/F4T)[T&(v2+&-dbc)] / accordingto differentcubicequations

- 0.47bJ

(7) (8)

(A~- AU,t8)/RT -2.319 I@ - 0.47bJv) = and using the following mixing and combming rules, b~= (1/4)(3~ ~ xixjbij ~ Xibii) +

(9)

Equationof State

d?

Vud,,h

ij

VanderWads Heyen Peng-Robimn Redlich-Kwong

0 al

0.581
0.806 0.833

where;

bfi= (bU ~j3+ b~f3;/8

Obtcl
o

blc
o

1/2

0.893

Eqs. (7) and (8),joined with eq. (9), are tested extensively for discrete as well as polydisperse repulsive mixtures and it is shown to be in very good agreement with the 652

WE 26667

M. MOHSEN-NIA, H. MODDARESS AND

G.A.MANSCXXU

accurate, but complicated, MCSL11repulsive mixture equation for v/b > 0.7, We have calculated the thermodynamic properties of equimolar binary mixtures (X1=X2=l/2)with (bzJb11)1j3 = 1.5,2.0,2.5, and 3.0. The results of these calculations are compared with the accurate MCSL repulsive mixture equation of state as reported in Figures 3 and 4. The maximum percentage deviation of the binary repulsive mixture compressibility factor and excess Helmholtz free energy for molecular diameter ratios of (bJbl#J3 = 1.5 to 3 is calculated to be 3% for v/b >0.7, which is in the range of accuracy of MCSLequation. In order to test further the accuracy of the proposed repulsive term of the mixture equation for multicomponent mixtures we have used it to calculate thermodynamic properties of polydisperse (continuous) repulsive systems through different distribution functions f(r). Following the method of Salacuse and StelllGwe can express eq.(9) for the polydisperse systems as the following bm= (1/16) (7%+ ~mJ (lo)

We can calculate the compressibility factor and Helmholtz free energy of this polydisperse repulsive mixture by joining eq. (16)with eqs (7) and (8), For the Schultz distribution: fs(r) = -J-(@)s r + 1 # [-(Q ) r] r (17)

where ~ is the first moment of the distribution, and s is related to variance of f.(r) by, y2 q(r) = var(r) = ~ 5+1 (18)

we can derive the following expressions for the b~/v of the Schultz polydisperse repulsive mixture b#v=4 ( pNOp)(@+ 2)(8s + 15), 6V 8(s + 1)2 (19)

Where, ml, ~ and m~ are the first, second and third moments of distribution function, respectively, defiied as: ~= [o For the normal distribution: f~(r) = (1/2rr@t12exp[-(r- i)2/2q ] the moments are given by rq=i + (2q/lr)l~ q= F* +q + 2(231n)*/t / ~ =~3 + 2(2/2r)~l~3J2 3q ~ +3~2(2q /rc)112 + (13) (14) (15) (12)

lhenby replacing this equation in eqs (7) and (8) we can calculate the compressibility factor and Hehnholtz free energy of the Schultz polydisperse repulsive fluids. We have calculated the thermodynamic properties of polydisperse repulsive mixtures obeying the normal and schultz distributions. The results of these calculations are compared with the accurate polydisperse MCSL repulsive equation of state*l in Figures 5 to 8. According to these figures the deviations of the multi-component repulsive mixture compressibility factor and Hehnholtz free energy for Shultz (with ~=1 & q =1/3,1/6,1/11) and normal (with ~=1 & h=O.1,0.3,0,5)distributions are quite low and acceptable for v/b >0.7 range of interest in industrial equations of state. We have also made calculations for values of ~ other than unity with similar results as to Figures 5-8 which are not be reported here due to space limitation. At this stage we propose the following modified equation of state Z= Pv/RT ,, (vz+.h-ci!bc) (2o)

ri f(r) dr

(11)

where q and ~ are the variance and mean, respectively. Therefore, the mixture b~/v, eq. (10) for the normal distribution is as the following bin/v = 4(@#)
[1+ (~)(~~

= (v+O.62b)/(v-O.47b)-(av/RT)/T

rn

+ ( 1.875x + 2.25)q + (~(a)n]

lrP

?C

(16)

The difference between this equation and the generalized equation reported in Table 1 is the replacement of the new repulsive compressibility factor given by eq (5). Provided the proper numerical values of E, ~, m-idd? are replaced in this equation one can reproduce the new versions of the equations of state

853

.}
4

A SIMPLE CUBICEQUATION OF STATE FOR HYDR0flARBON5 ANDOTHERCOMPOUNDS

SPE 24667

reported in TabIe 1. It should be pointed out that this change of the repulsive term will not keep the PengRobinson and Heyen equations in cubic forms anymore.

volume and contains only two constant parameters. By applying the critical point constrains, we determine parameters a and ~ as the following

By applying the critical point constraints: a =0,48748R2TCS2 and b =0.064662RTC /FC /PC (23) (~P/ilv)~C=(ii2P/~v2)~C=0for all equations); ~d Z = ZC ( The critical compressibility factor ZC=0.333will remain (for the three-parameter equations like Heyen) we can the same as the RK equation of state. In order to derive expressions for parameters of the new version of demonstrate the validity of the repulsive term of this equations of state with respect to the critical properties equation of state we have calculated v~#b as reported as reported in Table 2. in Table 3 for different fluids. According to this table for ali the fluids studied vm,#b values are in the allowable Xhkl@ Parameters of eq. (20) with respect to the range of v/b >0.7 where the repulsive part of eq.(22) critical properties, accurately represents the MCSL repulsive equatkm of state. 2,= FCvC/RTC y%: H Calculation of the minimum v/b ratio a/RTCvC b/vC c/vc New Original for different fluids according to Eq.(23) Fluid
Van der Waals

wdb 0.76 0.76 0.73 0.80

0.73

1.429 Heyen 1.94$ Fkng-Robinson ~.%l Redlich-Kwong 1.513

~ese

Mu o 0.371 0.997 0.370 0 0341 0

0.364 0.27 0.272 0.314

0.373

0.27
0.3U7 0s333

valuesare based on ZC=027.

According to this table, except for the Heyen equation for 0.73 Nk3 which ZCis an input parameter, the ZCvalues calculated based on the h@VV version of the other equations of state are closer to the experimental ZCvalues than the ZCS Extension of equation (22) to mixtures will take the fol[owing form: calculated by the original form of the equations of state. (~ ~ aij)/RT Z=~=v+l.31918M. - I j (24) T1/2(v ~ @ + THE NEW TWO-CONSTANT-PARAMETER CUBIC V-&m 1 EQUATION OF STATE By replacing d =0 in eq. (20) it will become a cubic equation in the following form
Z= (v -t 0.62b)/(v - 0.47b)- (a/RT)/fi(v

Ethane n-Butane n-Propane Oxygen Isobutane Ethylene NzOd HS

0.80 0.89
0.86

and

+ ~).

(21)

.+ b,j=(5,,1/3 &j;/3)3/8 and

aij= (1- ki,)(ai,aj~.

l%e choices of E and ~ are still in our disposaL For the sake of simplicity we choose ~=1/2, as proposed by Redlich and Kwongl, and 4=0.47b as appears in the denominator of the repulsive term of q. (21). As a result we introduce a new cubic equation of state in the following form
z= (v + 1.13191)/(v -8) - (a/RT)/T1i2(v +8)

(22)

Equation (22) is a cubic equation of state in terms of

In eq. (24) we have applied the new mixing rule for repulsive term (eq. 9), For the attractive term, we have used the usual cubtc equation rnixiig rules in order to be able to observe the corrections in the repulsive term of this equation for mixture calculations. It should be pointed out that there are also other possibilities for the mixing rules of the attractive term of this equation of state17. This new equation of state is used to predict properties of pure fluids and mixtures as it k reported below.

654

..

iiE26667
M. MOHSEN-NIA, H. MODDARESS AND GA. MANSOORI
5

RESULTS AND DISCUSSION

Cubic equations of state may be classified into two categories: (i) Those with two constant parameters like the van der Waals, Berthe!ot, Dleterici, and RedlichKwong (RK) equations. (ii) Those with more than two parameters (or two or more temperature-dependent parameters) and they include the Peng-Robinson, Heyen and SoaVeequations 1-7.Among the first category of cubic equations of state the RK equation is still considered to be the most accurate equation of all. As a result in order to test the accuracy of eq. (22), which is also of the first category of equations, for prediction of the properties of pure fluids and mixtures it is compared here with the RK equation. Table 4 shows the comparisons of the result of density calculations using eq. (22) with the RK equation and the experimental data. According to this table the result of eq. (22) are generally superior to the RK equation for 17out of 19pure fluids tested. In order to test the applicability of eq. (24) for mixtures, we have used it for calculation of the properties of a number of systems. In all the calculations reported here for eq. (24), and for the RK equation, we have chosen the value of the unlike-interaction parameters, kijs,equal to zero. This choice of kij=O is made in order not to complicate the comparisons of different equations of state with the fitting of their ki~s. However, for more accurate calculations of mixture properties this parameter may befitted to some mixture data. On Figures 9 and 10 the density calculations for two different binary high-pressure (500 bar) liquid mixtures (n-octane + ndodecane and n-decane + n-tetradecane) are reported and are compared with the results of the RK equation. According to these figures predictions by eq. (24) are better than the RK equation.
We also have performed volubility and VLE calculations

As it was mentioned earlier , in all the calculations reported here, the unlike interaction parameters, k,~s, are assumed to be zero. By choosing appropriate non-zero kij values the proposed equation of state would accurately correlate and predict properties of the mixtures reported in thk paper. The Icjjdata bank for this equation is not reported here due to space limitation. The proposed equation of state maybe made even more accurate by choosing its parameters (a & b) to be dependent on temperature as it is usually done in other industrial equations of statel-. ACKNOWLEDGEMENTS This research is supported in part by the National ScienceFoundation, Grant No. CTS-9108595. NOMENCLATURE A= a b c fz(R) K,i NO P= R= r F= T=
x
z=

= = = = = .

= =

for mixtures. On Figure 11 the volubility of methane innhexane is reported versus temperature at two different pressures of 40.5 and 81.1 bars. According to this figure also the predictions by eq. (24) are closer to the experimental data than the 12Kequation. In Figures 12 to 14 equilibrium pressure-composition diagrams for methane + n-decane (at 344.26 K), carbon dioxide + n-decane (at 344.26 K), and for nitrogen + carbon dioxide system (at T = 270.0 K) are reportwi According to these three figures the predictions by eq. (24) are far better than the predictions by the RK equation.

Hehnholtz free energy attractive constant in equation of state repulsive constant in equation of state third parameter in equations of state distribution function binary interaction parameter Avogadro number pressure Universal gas constant random variable the mean value and first moment in normal and Schultz distribution function respectively absolute temperature mole fraction compressibility factor a parameter in Schultz distribution function, defined in eq.(19)

Greek letters = density P z= 3.1415927 variance of normal distribution function l1= Subscripts = c i,j = ij = ig = m= N= critical property component indices property of i-j interaction ideal gas property mixture properly normal distribution Schultz dist~bution

..

,.

A SIMPLE CUBICEQUATION OF STATEFOR HYDROCARBONSAND OTHER COMPOUNDS

SW 26667

REFERENCES

1, Eclmister, W.C. and Lee, B. I.: Applied Hydrocarbon Thermodynamics, Gulf Pub. Co., Houston, TX,1986. 2, Elliot, J. and Daubert, T.: Revised Procedure for Phase Equilibrium Calculations with Soave Equation of State; I &EC Proc. Design & Develop., 1985, vol 23, pp.
743-748, 3.

12. De Santis, R., Gironi F., and MarreIli, L,: VaporLiquid Equilibrium from a Hard Sphere Equation of State: Ind. Eng, Chem. Fundamentals., 1976,15,183. 13. Kim, H., Lin, H.M., and Cimo, K.C,: Cubic Chain of Rotators Equation of State, Ind. Eng. Chem. Fundamentals., 1976,Vol. 25, No. 1,75-83. 14. Scott, R.L.: Physical Chemistry, an Advanced Treatise, Henderson, D., cd., Vol. 8A, Chapt. 1, Academic Press, New York, 1971. 15. Haile, J.M. and Mansoori, G. A.: Molecular-Based Study of Fluids, Advances in Chemistry Series, Vol. 204, ACS, Washington, D.C., 1983. 16. Salacus, J.J. and Stell, G.: Polydisperse System Statistical Thermodynamic, with Applications to Several Models Including Hard and Permeable Spheres: J. Chem. Phys., Oct. 1982, 77(7),3714-3725. 17. Mansoori, G.A.: Mixing Rules for Cubic Equation of State; ACS Symposium Series 300, 1986, Part 15, 314330,, Washington, D. C. 18. Takagi, T,, and Teranishi, H.: Ultrasonic Speed and Thermodynamics for Binary Solutions of n-Alkanes Under High Pressures: Fluid Phase Equilibria, 1985,20, 315, 19. Shim, J. and Kohn, J.P.: Multiphase and Volumetric Equilibria of Methane-n-Hexane Binary System at Temperatures Between 110and 150C~J. Chem. & Eng. Data, 1962,7,3-8. 20. Reamer, H.H., and Sage, B.H.: Phase Equilibrium in Hydrocarbon Systems, Volumetric and Phase Behavior of the n-Decane+Carbon dioxide System} J. Chem. Eng. Data, 1963, 8,508-513. 21. Reamer, H,H., Fiskin, J.M., and Sage, B.H.: Phase Equilibria in Hydrocarbon Systems, Phase Behavior in the Methane-n-Butane-n-Decane System, Ind. Eng. Chem., 1949, 41,2871-2875. 22. Somait, F.A. and Kidnay, A.: Liquid-Vapor Equilibria at 270 K for Systems containing Nitrogen, Methane and Carbon dioxide: J. Chem. Eng. & Data, 1978,23,301-305.

Du, P.C. and Mansoori, G.A.: Continuous Mixture Computational Algorithm of Reservoir Fluid Phase Behavior Applicable for Compositional Reservoir Simulation SPE Paper # 15953,Proceedings of the 1986 Eastern Regional Meeting of SPE and Proceedings of the 9th SPE Symposium on Reservoir Simulation, Society of Petroleum Engineers, Richardson, TX, 1986. 4. Benmekki, E.H. and Mansoori, G.A.: Minimum Miscibility Pressure Prediction with Equations of State; SPE Reservoir Engineerin&, May 1988, 559-564. 5. Chorn, L.G*and Mansoori, G.A. (Editors),: CT+ Fraction Characterization Advances in Thermodynamics, Vol. 1, Taylor & Francis Pub. Co., New York, N.Y., 1988. 6. Mansoori, G.A. and Savidge, J.L.: Predicting Retrograde Phenomena and Miscibility using Equations of State~SPE Paper No. 19809, Proceedings of the 1989 Annual SPE Meetin& Society of Petroleum Enginews, Richardson, Texas, 1989. 7. Ahmed, T.: Hydrocarbon Phase Behavior, Gulf Pub. Co., Houston, TX,1989. 8. Kawanaka, S. Park, S.J. and Mansoori, G.A.: Organic Deposition from Reservoir Fluids SIE Reservoir Engineering Journal, May 1991,185-192 9. Escobedo, J. and Mansoori, G.A. Heavy Organic Deposition and Plugging of Wells (Analysis of Mexicos Experience),: Proceedings of the II LAPEC, SPE Paper # 23696, Society of PetroIeum Engineers, Richardson, TX March, 1992. 10. Redlich, O., and Kwong, J.N.S.: On Thermodynamic of Solutions V: Chem. Rev., 1949,44,233. 11. Mansoori, G.A., Carnahan, N.F., Starling, K.E., and Leland, T.W.: Equilibrium Thermodynamic Properties of the Mxture of Hard Sphere: J. Chem, Phys., 1971,54, 1523; see also Carnahan, N.F., and Starling, K.E.: Equation of state for nonattracting spheres: J. Chem. Phys., 1969,51,635-636.

656

..
.

Tsbla 4 t Co2persimt of prediction for density

of diff~rmt
Pr**ur*

this

work

and RX

empounds,
NO. of Oata

q qttrttiorm

of

stato

SPE26667

Crmpmmd

Tespar*turo Itotriw, (30

Range, {As)
40-400 5-400 1-215 10-700 5-500 10-700 5-700 10-600 10-600 5-400 1-.900 1-500 1-500 15-1000

w 3.9 1.8 5.0 3.4 1.9 3.0 3.1 3.3 4.6 3.1 9.7 6.s 6.3 7.9 8.8 10.3 11.3 13,3 1s.6

%wo3rn 2.4 2.2 2,6 2.B 1.7 3.4 2.6 3.1 3.9 2.8 3.3 2.8 2.2 2.6 2.5 3.2 3.7 4.7 6.4

C02 H2s S02 fiz &rmO PropOn* i-Butm3* n-PMMna Nerrptano n-tfexarm n-li*ptenO n-cmtena n-ttmrsrm

n-oecann

2BO-1OOO 300-700 2!35-500 200-1000 200-1000 91-500 200-700 200-700 300-650 300-600 298-1000 300-1000 320-1000 300-600

300-500

15-500
50-1000 1-600 90-1050 1-600

n-Und8aanIa 200-570 n-oadeaanm 200-570 n-Trideoen*300-570 n-cl 5 310-410 Ov.ral 1

143 101 115 183 120 170 140 130 160 60 100 130 80 90 130 40 20 00 30

1992

6,2

3.1

4, 3.

26

.82
/

2. 1-

If& q
-%, %,

1,6

,<,,. ,#,,*
,/ ../ ,/ , #/,,/ ,,**

,~

-1-2

%, %,,, %, %,

#_ ...
Eq(d)

s,

Eq~

e 4+ o am 01

/ *P %,, ,,,,,,,, ,*#J \+

A@
Mm ttt.a ,,,,,,,

SCOT Cs

SCOTT am CM a25

aa

a26

c#tl

ac6

al

a\6
Rrmiwd

a2

Rfxiuctsd Denslly
Ff&arr 1. TM prrrmtsge davfaffon of comprrmlbillty fmlor from the qxact MCSL frstd.zphrrs eqrratfon of smte venue the rrducad dmd~. WvL for th~ Pure hatd spbare-flutd. -

QZEI OensfW

a3

a3s

I 4

Ffgura 2. 211c excasa Helmholtz free enm& awmflng to different approxlmatfonz utd the exact MCSL fmrd ephere equ.et mr of stao? versus reduced density, fr/(4v), for the pura hard sphete fluld.-

4> s 2.
q

I.e 1.6 1.4 I

ji

1./ Q -q .... &?/dll ...*a 1.6 ,/

q **
) i #

-1
a4

~,,a,s.~$: ::)
ah da
am
at Reduced Density
Fl$um 4- Tfm excess Helmholtr free ene~ q ccording to Eq. (9) and the exact MCSL qrmf{on of etate vema the reduced denelty, (btl+b#W for hard sphere mixture q the bhrary mixture hard sphere fluid With (b~bj)a ~. For %fit~s ta~lo~ ltia than 3 the two theorfea would match even better

Ffguas S - l%e pertcnfage dwiatlon of cmopmmlbllity fmtor from the easct tnfxtww MCSL bard sphrrs equatfon vmmu the Qhrtum zaduc6rf density, th,t+b#W), md ferdfffermtt mtrlccufsrdbetetett etim fvrbkmry mlxterazof hzrrf sphere flufde.

thanthfa reported care.

W7

-= Ver. =
o

a60

am

al

Calff a2 t126 Reduced DensItv

LL3

cl=

I
a4

Reduced lXrnrJty
Figure 6. The excece Helmholtz mixture equation free cnerffy according to t?q. (9) and the exact MCf6L dcnalty, (n/6)N@mv would for with mean valae of match hard ephere of attte vcrvua the reduced

Flgrcnr 5. The percmrtagt devkatlon of compressibility factor from the exsct mixture MCSL hard sphere cquatfon of state for the polydl!iperae hard sphere rrrlxhcrc with normal value dlstribul[on, vecatra the mixture vmlances. reduced density, (nf5)N@mY and for mean of F = 1 and dlfferznt The third

moment, my of the normal

the polydlsperae

hard sphere mixture

with normal dlstrlbuNon

dktrlbutlon la dcffnedby eq.(18).

i = 1 and variance = 0.5, For varfances even better than thle reported caae.

less than 0.5 the two ?heorlca

: % #-* .. -1 \ J
9 ,8

MCX%(W =1/~ ../

2
+
s 1.6

M&wr.=1/11)
E;(EMvw.=1/q E:(Q,@=l/11) 9 ,,? ,,,9 * * ,9? ,9 * ,p * + + *

,9
*P
56 .+

,$

~ s,

.4

Wu.=l]a

-z ,,,,,8,

N ..:

Vat.=m .-..

..*

-.-d

% *,

Q ;/

~,,,y

Laoo

al

als

Li2

Q26

ci3

cA3a

Reduced Density
Flgurc 7- The percentage deviation of hzrd.epher mixture compree$lblllty factor from the exact mixture MCSL hard sphere equation of state for the polydlsprcse hsrd sphere mixture with Shultz distrlbutlon, versus the mixture reduced density, (d61N#h+3)($*2)/1$+1):, and for mean value of ~s 1 and dlfferant varlancea. Figure 8. The excaas hard.sphere m{xttwa HelmhoIk free energy accordlnB to @q. ( and the exact MCSL hard sphere mixture equatfon of state vecaus tht reduc{ density, (ti6)N#(s+3)ls+2)/lt+l)t, for the polydlsper$e hard sphere mixture = l/S & lfll. with Shul

distclbutlon

with mean vafue of ~ E 1 and variance

10

#
== 0- .... ... .. .. ........... .. . .. ....... :
c

m.

4
R( NEW

o-

. .. . .. . .

. .. ...... ..... .... . .

...

. . . .

. .

. . .

. . . . . .

. .

,...

. . . . . . ...4

= -10=
e o = ,g g 43 0
q

z = -1o0 =
9 s g -20is

FK

NEW

-30

0.0

0.2

, 0.4

0.6

0.6

1.0

-30~ 0.0

0.2

0.4

0.6

0.6

f .0

Ffgrme 9. Tire calculated percentage devlatlon of (n-octane + ndodecane) Ilquld mixture density fmm the experimental data [18L accordhrjj to the present and RK miaturc cqu&rM of state O@N, vemus n.doclecane mole fraction at T.298.lS K arrd P=SOObar.

Figure 10. The calculated percentage devlaNon of Iccdectarre + n.tctradecane) Ilqald mixture density fmm the cxparfmentd date [18L accordhrs to the present and RK mixture equatlona of state fki~O), venue n-tctradcmrre mole fractfnn qt TD29R15 K and P=5W bar.

SPi26667

!+----1.0
z

P m 40.5*. P = 81.1 biw

NEW NEW

., ,.....,,.. -*-sI*---1

FO F

m. Et@

NEW 120 100 80

m o

T .344,26 o

... ... ............. .. . ........ . ........................ ...

80

/
1

1!
0.0
200 ~so Temperature

40 ~
20

K 300

.[,
0
0:2 0:4 0.s

.,.
0.8

+
1.0

Figure 11. Pccdlctiom of the euhcbill of methane !/ pce$ent and RK mlxtute equations o -tetc (ktrO),

10 ct-hcxsne accordln$

to the

vecmm temperature St two different pretmcres.The experimental data ceported00 this graph am taken from
FlgcIra KC. Prediction

(X1), (Y1)
of the equilibcham prcssum-composition ia~m for [czrbon d dioxide+ n-decane)systemaccording Me presentand ~ q to qUa@M Of ~ta?e mJ@)# data mpoficd On fhis ~ph are !ak~n fmm Raf.

Ret [19L

at 34L26 K. The expccimcntd

[201.

l
3000

w
Elcp. o

2oo-

1000
*

[
0.0

EXO I
0. I

Q
[ 0.s

I
0,2

i
0.s

oo~
(X1),(Y1)

I 0.4

1.0

(xl ),(Y1)
FI ure 14 . Prediction of the equiIibrhcm pressure.compu.sltion dfcgram for (n ! trogen + carbon dloxfde) system according to the present and RK eqccatione of state Cc,r=), at T M 270 K. The experlmentaf data reported on this graph me teken from Ref. [22f.

WCC 13Predlctfon of the equilibrium premurr.composition diagram for (methoe + ndecacre) systcm accordici~ to thr pra$mct and RK equations of Stat* ~ ), q 344.26 K. llw expecfmmrtaf data cepoctcd on this graph are tafwn from Ref. El!?

664