l?

"-" Ar:
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R-'i

PAPER NO. CIM6PE 90-i00

SS3J%a""""- suBJEcT'oco"Eo"oN
A ROBUST ALGORITHM FOR
DETERMINING HYDROCARBON PVT
PROPERTIES USING A
GENERALIZED EOS

BY
Fawzi M. GuahrLa /
Laslle a. Thompmn
Almrt C. Reynolds
Tulaa univ*rmRy

PUBLICATION FIIGKTS RESEFiVED

THIS PAPER IS TO BE PRE"hENTED AT THE INTERNATIONAL TE6'HNaAL &AEETING JOINTLY HOSTED BY THE
j!E?.K4! EuM sxxwes-z asf;t ?try OF PETROLEUM ihaihetns IN CALGARY, JUNE 10 TO 13, tggo
alSCuSSION OF THIS PAPER tS INVITED. SuCH DISCuSSION MAY BE PRESENTED AT THE MEETlNa AND WILL BE
CONstoEREo FOR PUBL?CATION IN CIM AND SPE JOURNALS IF FILED IN WRlnNa WtTH THE TECHNICAL PROGRAM
CHAIRMAN PRIOR TO THE CONCLLIS?ON OF THE &lEEnNa.

ABSTRACT whether the systez temperature is ygestex or lem than the

This paper p?ts aod d3ac? h complete phase
behavior package for determining PVT propatia of mix-
turm of hydrocarbon rod non-hydrocarbon specia com-
monly encountered in the Petm!eum hidustry. All cai-
culations ue perrormed using a generauzed Equation
Of State, which upon selection o{ appropriite puune-
ters, cmx be used to represent axxy or five Equations Of
State commonly employed in the Petroleum Industry; i.e.,
Redlich - Kwong, Zudkevitch - Jof!e - Reaidi - Kwong,
Soave - Redlich - Kwong, Peng - Robinson uid Schmidt -
Wenzel,
A robust aJgorithm, which utilizes a combination or
the modified successive substitution and Minimum Vari-
sble Newton-Raphson metho&, is ? to caJculate flash
cozposition and saturatiori poir.ts. The algorithm is opti-
mized to facilitate convergence near the critical point. The
i
crittcal temperiture. The method doa ? require estj-
mation of the critical temperature for the specified mix-
ture. Straight forwaxd application or a method proposed
by Baker and Luks allowm the user to efficiently compute
ah mturation points (i.e., a bubble point and a dew point,
or, an upper dew point and a loww dew point) at a given
value or temperature. This latter unique feature enables
the user to define the two-phase envelope without havirig
to perform a multitude or time consuming fiash calcula-
tions. Finally, results from oar phase package are com-
pared to those pragented previously in the literature in
order to ver;fy the accuracy and efficiency of the cozpu-
tational procedure.
INTRODUCTION

modified successive substitution method is used to deter- Calculation of fluid properties and phase equilibria Li
mine the number or phases present at a given pressure asid important as a general petroleum engineering tool- Nu-
temperature. A new simple method is uned to ascertain merical computation oF phme equilibria using Equations
I

too-i
i
J?. a'("Ys7"T"'ii'i *i ;m-? ?- =-' - " ""'= ' "- a """ 'Ft? ?' - ' ' """% " " a'

, of State is very important because lai'borztory analysis is GENERALIZED EOS

' eXPenSiVe aJld time COn8uming- In this major tion we ahow thit all five Equations
In this work, we discuas a robust phase pw.kage that of State considered here cam be written in one genenJimi
' can be used to perform phaae equilibria caJculations based form.
on any of five Equations of State commonly used in the oil Notation and Mixin ulai
, industry; thit is, the Redlich - Kwong' (RK), Zudkevitch - We consider a mtxture composed of Ne hydrocaibon
Joffe-Redlich-Kwong"(ZJRK),Soave-Redlich-Kwonga andnon-hydrocssbonapecis.Definea<andb<aafollo'ws:
' (SRK), Peng - Robinson4 (PR) and Schmidt - Wenzels (z27n,
' (SW) Equations or State.a<=rla,4-5A,
Pc,i i=l,2,..jVc; (1)
The package is designed to enable the user to generate RTclt .
a wide variety of fluid properties, such as denstties, com- bi Pe,i
"' nb,t ! "'a 1s2s-Nc: (2)
pressibility factors, and viscosities. Moreover, the package where Te,l'i Pcit'i $1,,,I. ,,3 (,bli ,, mp,tiyely the ,itic&1
OfferS !he OT)t!On Of -using onei or a combination of two temperature, criticaj press'ure md van der Waals coeffi-
numerical techniques to solve the single-stage separation cients for component i. In Eq. (1) n = 2 For the SW, PR
i equations that describe the thermodynamic equilibrium or and SRK EOS's asid n = 2.5 ror the RK asd ZJRK EOS.
fluidsi depending On whether the mixtures considered g6 The phase m mixture parameters a,, and bm are de-
single phase, single phase saturated, or two phase (liquid fined ' follows:
andvapor). grt,
The first numerical technique is a special version or a" a I L z'i'zji'a'j ; (4) i
i the coawonly known successive substitution methoda. Its '
N,
i=l j=l

j preSSure,region
phase and its simplicity.
withoutUnfortunatelyi
having tothiscompute
method where thea43 is determined,=1
aaturation from, two
thema3ot
following
adtagesrelationship:
are its abuity to detect the smgle , .-w
, converges very slowly (or not at ill) near the critical re-

bm"%<,is(S)
,' gion. When the successive substitution method is converg- a'i,i a (1 - kij}n- (6)
ing slowly, our computer program automatically switches . .
i to a more robust technique cal)edj'For
cthe the Minimum
; (valuaRK
of a<ands used
ZJRKm each
equations,
Variable ai = 1,for,Equations
of the remaining ,1 <, s, S
,' New'on "p"n (MvNR) methody. of State considered axe provid*d in Appendix A).
i

.' phase
The 'flregion
;ay be used aexcl'usively
is known prSded
priori. In this C&8ei the
the pack-Inorieraction
Eq. (6),pyametex'
thei and
terj.that
&<4 is represents the
ipecific to binary s'6p %
mixtures
age is capable or determining the saturation pressure p,aH components k<3 is assumed to be indepen-
l

3Hd l)16 6qpili%yiHz z@16 {yi'l@B (@zp(;6ili@y1 @{ l%6 p%6 (lent Of the &Ctu21l nCliXtuFe COmpa!l!t!On, 8)'8km pra5!+ure
that develops &t p,at, {z<}{,..N-1 or 4,yi}l,%.N*1 vvfiey6 g iB %%e &nd S)'8kenn ke!perakure aJld aL5 dele!aZnlned fTOna eXPera)- i
riumber o(;vdcomponents
pressure temperatureithatthecharacterize
pachge alsothecanfluid.
perform
Givendescription
mental dataof on
mostthemulticomponent rntxtures-the
particular i-j binary. It u usedma5or
tn the
a constapt composition flash calculation to determine the
. . . assumption being that higher order interactions (e.g., be-
tween components j, k, and l for ternary systemi) are
liquid and vapor compositions, asid the mo!es of liquid negligible. Most Equations or State deve)oped , recent
hnd moles of vaipor per mole or fluid mixture at any pres- yearsi and , particu)as those that are co,iae,d in this
'Sure- F;nallY+ khe Pa':kage uSeS COffelak;OnS !O de'er'ne work, take the binary interaction parameter into azcount.
atvre and phase compositions. EOS may be SVhile&;,7isasmallnumber,theresultsobtainedfroman
thephaseviscosities8-11asfunctionsofpressure,temper- very sensSt;ve to the value used for k,312.

100-2
-:-'r>' "'= o""-' =fm'f'm"i""?"' " 'T=""]"="=" "-" , '11
a?t..l(.,, ,7-@By?z?'?l+(=
T
l
i

In all casai, k<,4 % taken to be xro. h'i the RK EOS ZJRK EOS: U ==. 1; W = 0.
k<,; = O ror 1 < ij < Ne. Fluid compreaaibility {Z-}fwu>r % defined (based on
h'i Eqs (4)-(S) asid throughout, z<,m denota the mole the Engineering Equition of Stak) aa:
fraction of component i in phme m, m = L for liquid and 7m
m = V for vapor, but we aJso use z< aa the mole fraction of Z,, e-. (10)
RT
component i in the liquid phase sod y4 u the mole fraction
The Generalized Equation of Stite (Eq. (7)) may be 'recut
or component i in the mpor phase, i.e., z<,z = z4 uid z<,y
in terms of phase m fiuid compreasibility Eagtg*r (2-) to
= th.
yield the following cubic equation:
In terms of the noktion introduced in thia aection,
the generalized EOS caw be written in the form: Z-a - (B,. + 1- U8,,) Z,,'
RT affla(Tlw) + (A,, - UBm - UB,,,' + WB,', ) Z,
p a :- ivffl2 + Ubfflvffl' + Wbffl2 ) ; (7)
-(i,,,n,,+wn,,2+wn,,,3)=o, (u)
where p is the pressure in psia, T is the temperature in oR,
R 4 the universal gas constasit, (z 10.73 part - ft8/lb - where U, W were defined previoualy, rod A,, B,,, are given
by
moJeoR), v,,, ia the specific voJume ( fta /lb - mole) and U amP
and W are pasametera whose valuai depend on the EOS ffl -- ?s
72ja (12.1)
selected. The function a(T,w) is defined for ez? EOS in and
bvrsTl
Appendix A. B,, :-. (12.2)
RT
For the SW EOS, U and W are independent of tem-
Equation (11) may be sohred anJytically for & max-
perature and ye related to the mixture acentric factor,
imum of three reaJ roots. In the mo-phase region, with
gm<, as follows:
m = V in Eq. (11), mpor compremibility fbctor Zy is
U =- 1 + 3wmizs (8.1)
assumed to be the largat rew>t; stmilarly, with m = L the
and smallmt root of Eq. (11) u the liquid comprmsibility fac-
?- W = -3wffl<,,
IfW???-:-- -. (8-2) tor. Au remaining roots are without physicaJ significance.
?

where the phase m mjnure acentric factor is defined as The fugacity of component i m phaeie m, (/,;,,) * a
measure oT the tendency of the component to scape from
Wmiz ""a
ziN;1 w4zt,mb?'. (g)
the phase, When multiple phases coexist at equilibrium,
14,N'1 r'lmbo<a' the fugacitia of each componait in each phase are ? tt
equilibrium. The ?ues of Zffl cJculited from Eq- (11)
In Eq. (')) w4 it the acentric factor ror pure component i.
are needed to emluate the fugacities d each component in
Our phase package computea w< using the following defin-
each phase. The reler?t equation is:
ing equationl2:

w4 =-1- lOgpvp,t,ia ST"i,m / Jw laNi,m Vm )

-nrhZms (13)
Here pyp,rl< is the reduced pressure (p@@4,<lp@,<) or satu-
rated vapor evaluated at the reduced temperature T/Te,6 where N6,ffl xd Vffl rapectively denote the number oF
= 0.7. The saturated mpor preasure is computed via Rer moles of component i in phase m asid the volume of phase
del's vapor equationl3. m.

U and W for the remaining Equations of State are con- The integration in Eq. (13) cam be carried out in
stants (i.e., independent of uffl<,). The appropriate values the following manner: (i) evaJuate the partiJ divivative
or these parameters are as follows: of pressure with rapect to the number oT moles of com-
PR EOS: U = 2; W = -1. ponent i from the EOS (Eq. (7)); (ii) integrite, and (iii)
SRK EOS: U = 1; W = 0. use the cubic (Eq. (11) with the appropriate definitions
RK EOS: U = 1; W = 0. of Am and B,, to obtain a generalized expression for the

i, i oo-s
 l --+'h'fflfi7'@ -?i ?-'. r-'!"?'?"OY"Q'M?'y. v. r*'MA"fsss., + mq -a+v*a?37my? r . 7%.%a%l
.#x*...a

l -""'

partial fugacity of component i in the phase. The raulting N,

, expraision assuma the.following generdixed form: Xz< = 1, (17.2a)

i=l

ln (%p. ) :- ln (Z,, - B,) + -!" (7ffl - 1)

b,,,
N, a
lM4 = 1. (17.2b)
+
Am
ln
2%,, + un,, + Bm iml

n,,, zz,,, + un, - n,,, Note thit both ot equations (17.2&) uid (17.2b) can-
H, not be used beciuae, given one, the second may be
xh=s
r,,b<
am=
4'W2, ZhNl's
th,mai,h
3(U+2) + U2 =- l -
zbimboha'
b4o'(w;-W) derived by combining the given equition with Eqm.
/ ' 1-
, l B,,'U2
3 b@6'{w<-u) (is) md (ie).
%m
X
1
{2Z,,,- +- UZ,,,
4W +Z;;i zklffl62.y
2WB,,,
Equition (14),+reprsents .the partial fugacity
UB,). (14) (iv) Finally,
of com-the critaion for thamodynamc equilibrium:
ponent i for the SW EOS. It reduca to the PR, SRK and
RK uid ZJRK ca by aetting W4 - w = 0 xd by us- /i,L = /,v, 1 < < -5, N, (18)
ing the ippropriate coefficients Am, Bm (Eqs. (12.1) and where f4,z. im the fugacity or component i in the liquid
(12.2)), U uid W. Thm equation wiu be used' throughout ' pham at premure p uid temperdure T uid f4,y % the
the remda of this work. fugazity ot component < in the mpor phase it prssure
l

THE MOW'nED SUCCESSn/E SUBSTrfUTlON METHOD p md temperature T.

The condition of thermodynamc equiubrium between We have chmen to uae Eq. (18) sui our criterion for
!

i
i

coexisting phmes is described by the fouowing mathemat- thermodynamc equilibrium since fugacities ue easily ob-
icaJ equatiow:
tainible u functiona or preuure, temperature and compo-
sition from an Equition ot State.
(i) The overdl ma!erial balazce: Nghiem et d.a uaed the modified auccemive mbstj-
i

i L+V=1, (15) tution method ror the SRK EOS. In our phase package,
where L u the mola of liquid per mole or fluid mixture we hsive succmafully implemented the succeuive aubstitu-
and V * the mols of mpor per mole or fiuid mixture. ' tion method for ajl EOS's considered here. This method
may he used for detectmg the iingle phase region or per-
l'
, (ii) The component miteriaJ bce:
forming fimh eaJculations. Its main dimdvawtage is thsit it
i convagai slowly (or not it all) in the neighborhood of the
i i 4 = Lz< + VW, 1 :. i< Nc (16)criticaJ point. Whenever this problem occura, the progr
where {"i}is='l is the mole fraction composition of the switchm automatically to the robusrt MVNR (Minim'om
initWfiuidand {z4}iN.aland {y<},l"a azethemole VbJe Newton-Raphs+on) method.
fraction compositions of the liquid and gas phases re- We now provide a brid description or the Succemive
Substitution Method. Equitions (15), (16), (17.1) yd
spectively at preasure p asid temperature T. (Note (17.2a) or (17.2b) can be combined to give:
that Eq. (16) showa that z4 moles of component i, 4
when equilibrated, will be distributed as Lzt moles zs 1+V(K,
= . , 1)
l < i < N, (19.1)
of component i in the liquid phase and Vy< moles or
and
component i in the vapor phase.)
(iii) Mole fraction constraints: K<z<
N,
V, 1 + v(K, 1) , 1 < s S ye ( 19a2)
12, = 1, (17.1)
s=l
where K< = y</=<. The criterion for the thermodynamhc
equilibrium (Eq.(18)) can be rewritten as :
Fi = - = 1. 1 < s < N, (ig.:i)
fi,v fi,r. .

100-4
 k

It is aasy to me that the equilibrium K - valua are u r(0) >0 xd r(1) < Oaotve Eq. (19.5) for V,
related to the fugacitis vii the followtng equition : (7) Updite z4 uxd y4 from Eqs.(19.1) uid (F).2) stud go
to mtep (4)
%% m %, piL!, s <. i <. N, (19.4)
In the aingh ph? region, wha'e V = O or V = 1, the
Ui,Vhip) zi F<'s miy converge to & vdue diffeent thm unity. Ngh?
I A ma3or step in the succmsive mubstitution method is et aJ.a siugeat iteriting until Eq.(20.2) is mtmfied even in
I the solution of iingk phaae cwaa. Bowever, i * campu?na we haw
done, U r(0) < 0 (or r (1) > 0) it the maind itera!m (i.e.,
i r,)=ty,-L,,:: 4(A";-1)
i=l
L "-' -' ao
i.l s + V(A'4 - 1)
i=%
(19.5)
at the fird applmition of sttpa (4) snd (5), them r(0) < 0
(or r(x) > o) d sill sub?t it?iom.
i The ?t? d thjs proced? i thd it skms m
forV.
to detect the smde pbase region. Our plum pad?e ajso
l

uses thts tedinique to provide s rpmmabk inhial gum for

l

i
Succemrve Subditution Algorithm
F irsP iteration the MVNR methoa. In Eq. (X).2), we hiw ?ly uaed
t = 10-' for the e'rar tolaaance.
(1) Compute initiaJ mtim? of Ki from the following
?theoreUcal equsk?iorxl4:
MVNR METHOD
r / T,,Sl
Pe,ie?ls.37(l+u,')l1-
i xTii
' 11 The MVNR method was firtt prese? by Fumel affl
p
(20.1) Yusmik' aa & robust algorithm for we? the m>?
s7stem of equitions describiq th? eqtiilib;mn
(2) Compute r(!' = 0) uid r(V = 1) from Eq. (19.5). uging the ]!LK EOS, (see Eqa.(15)-(18)). 'The equ?
u r(0) > 0 uid r(1) < 0, we have two phum uid were sokved e3? tot mttirdion 7tewure xd camyxar
Eq. (19.5) is aohai (using Newton'i method) for V. tion of the torminz phme or plum compomitiam art fmd
Otherwm, (i.e,, U r(0) <. O or r(1) > 0) we may only tem?ure uid pmasure (ammmg ccwtma feed compo-
have & sing3e phaae prmait; in thisi cue, we assume & mition rod t)m two phaam exmt). Suxe M'VNR is & mamr
value or V = 0.5 and proceed with the cajailatmn. v'ariable Newtxn-Rhzpson method, tt requ3res the compu-
(3) Calculate z< and y<, rmpeetrvely from Bqs. (19.1) azid tation of partiaJ derimti? of each phaae fu?ity with
i
(19.2). rwpect to prmrure and p? compmUons. Altbmii
Subsequent iteratiomi other rsembers by* {ot simplicity, emtated these par-
(4) Compute f4,z and f4,v 'hm Eq.(14). Evfflua.te tial der?tmes using 'avmarml diffa'vntiitiom, they hive
f<,L aJso ?mted that improvai perto?ce of the MVNR
I

oo '?fi:v will be obt?ed V theae putW de'mti? are esrduated

i
and
azialyticaJly. Our pbase pa?e empkp xalyticaJ ertprear
'li sions for the .relemnt putial dermtives. Theee xalyticJ
K,=F,-.
Zi expreas;ons, which ? g:iven in Ap?dix B, were derived
i
(5) Check for convergence using the following criterion: from the ?erali? EOS (Eq. (7)) and to the beat oF
N.
our knowledge, have not been presented previously aCept
I

l(F; - l'l2 :S e. for the RK EOS'. Here, we do not repea?t the details of
(20.2)
the method; rather, we gimply provide axzalyt*al expres-
t

i=l

l sions for the relevant partiaJ derivatives when a generalized

u Eq.(20.2) is satisfied xtop - if not proceed to mtep EOS (Eq. [7)) is used to describe the phase behavior (see
i- (6)
Appen? B).
(6) Compute r(0) and r(1)
i As with all methods based on Newton's iteration, the
If r (0) < O tut V = 0, i.e., single phase liquid.
i

l
initiaJ (uem is critical to the succeas of the convergence
If r (1) > O set V = 1, i.e., sin.gle pham mpor. of the computations. For Flash caJculations, we use the

too-s
ls,,,,AJ ,)..s4mY{k%vH*sr- Ysr#,s;vasrts:,(W},fr&]*>-m-N,rPiPr,,:-k;A %-"P:l'z}4-"rFThfrq?rL - k"- "%n?'tY'P",.."?.o?'%:+-v AA'r? - '?r -a, c
Successive Substitutmn method (described ibove) with a
!arge value of t ( K 10-a) in Eq. (20.2) !o obtm our initial
guess for the phme compositions.
While sm %pper'mturation potnt (bubbJe or dew)
will admya exmt ror & two-phase mmure, the aaatence of
a 'lowd' dew point preuure i dependent on the shape of
the two-phase envelope on a p-T dia@mi. For &ll prxtical
purpoaes, petroleum engineera ue only interaited tn min-
imum premura in excms of & few hundred psi. Thus, we
hasre designed the following ? method of detarmining
(a) whether the %pper" mturition prewure im & bubble or
dew point pra+sure; rod (b) whether we vill encounter the
lower dew point pressure over normal operating pressures.
(This informition is vitaj in modeling the behavior or fiow
or multiple hydrocarbon components in Jl porous medium,
w'here in zitu fiuid composition mr* continuously with
time.)
?g that & tw>phase region exssta it the system
temperature (i.e., siystem temperature is to the left of thq
cricondentherm on & !)-T di?am), the method consists
of the fouowing aeps:
i) pedorm & Flaah caJculition (uaing the previously de-
scribed modified succmsive substitution method) it
system temperature amd a very high presaure (e.g.,
10000 psi) so thit we axe mured of itngle pbasp '8nid
'This determines the location of the system tempera-
ture relative to the ?ure critical temperature: i.e.,
U V = 1, the fluid is retro?e condensate; conversely
if V = O the fluid is black oil.
ii) Repeat Step (i) at the lowat mticipated ?tem pres-
sure; U O < V < 1, the lower aew point preasure is
of no practical significasice. Otherwim (if V = 1), the
lower dew point preasure must be determined.
The initial guais for determining upper and lower sat-
uration points employs the following method due to Baker
and Luksl6.
The phase m partiaj fugacity coefficient is defined u:
/i,F)l
(21.1)
p!Cilm
For a bubble point calculation, the x.<'s ye known (equal
, to z<'s for the overall fluid mixture in-place) and the mpor
phase composition is given by
1 < i <? Nc (21.2a)
100-6
ma
The dew point calculition amNog, of Eq,(21.2a) *
(T'k,vVi) % [ kv S
Zi2 - - i iVt* s -5. i <. N, (zx.#)
The method invoSves the following steps:
(1) pick a low premure (e.g., 1 pmi)
(2) Compute $<,'sr and $<,z zt the preasure of the new
iteration level using the composition from the old it-
eration level.
(3) Emluate the unknown phase compoaition using Bq.
(21.2a) for bubble point or Eq. (21.2b) for dew point.
If :j,N;1 z<,, < 1 then the aasiumed prauure is too
high, if not, the assumed pressure is lo*er than the
saturation pressure.
(4) Correct the pressure in accordance wtth atep (3). Baker
' - and Luks' recommend ati inrrpmpnf of 100 to 300 psi.
At thim atage, a bisection type method may be used
to narrow the aearch range.
(5) Repeat steps (2) - (4) until convergence.
The resulting phase composition uid pressure is then
used to start the p - % or p - y iteration or the MVNR
method. This procedure mevitably results in an %pper'
mturation potnt. The 'ktwer" dew potnt is obtained by
starting at the last Baker asid Luks atimaited %pper' sat-
uration point asd modt'fying the criterion of step (3) above
in the following way: 'd Z, z<,ffl < 1, the guased pressure
is less than the kmer dew point press'ue; otherwm, the
pressure estimate is too high.
MODEL VERIFICATION
The package has been extensively tested for each Equa-
tion or State and here, we compare our results with pub-
lished results.
Saturation points
Tables (1) - (5) compare saturation point computa-
tions from three Equations oT Siate, (ZJRX, PR and SW
EOS).
One of the modificataions made by Zudkevitch and
Joffe to the original RK EOS was expression or the van
der Waals coefficients n, and rl(,, as functions or tempera-
ture and acentric factor. Table (1) shows the computation
of the bubble point pressure (refenerl to stmply as pres-
sure in table (1))and the composition or the roming gu in
a methane/butane/decane system, using the ZJRK EOS.
We used the same set or binary interaction parameters as
 - '- - - '-- -" '-""
!F-
?
, ,,,= Wlitl.l.--fflillfl'%t-IafflaP 4M%%++l- ------. ..- ....
Ref. 16, i.e., k< 4 = 0, except for kl,2 = k2,1 = 0.024 uid
l k2,3 = k33 = 0.025 (Here, methane, butane asid decasie
are referred to ut components 1, 2 and 3, respectively.)
For T = 160o!, using the mme vaJus for n@ uid
n(, u Ref. 16, table (1) indic that the experimentaJ
i
l
and pe resultm agreed wtthin law than 3% for bubble
point prmsure. The K - vaJua computed fx oux pack-
u'e maentiaJ}y identicaJ to obtained by Rd. 16
azd in reasonabJe ament with Lffi reaulk. The
greatart dmsepancy between computed uid experimental
K - vajum occ'ars for the lighter m3Xbue (%l = 0.663).
To gate the T = 280oF mtiltm of Table (1), we used
the set of coefficmnta ariginJ]y reported by Zudkevitch
and J!e2; ha'e devid from the reported -
taj valuai weae more cuit. In generaJ, we foand thit
replacing the de Waals codlacienta in Rd.
17 by thaw ted by Cmta' proce yielded better
agreemait 'mh valua of bubble point premre obtffied
experimeatamy.
Tabffi (2) aaxd (3) thow the mturmon pomt eompu-
t m the PR and SW Eqions ot State, rwpec-
tive§. As *own, rea obtained from the package a@ae ' FamfflM.GuehriawtothamPPetm
very with the ramlts of Rd. 17.
The PR EOS was mai to a the varTh of the
bubble pomt md dew pomt of a mmure cmtaining thir-
hydrocarb6n compcments plus & concentra!ion ot CO2
rmging from O to 80% (See TaJoke (4)). T*k (5) shmrs the
rwultm for & stvesteai component m3xtuxe that includes
a ied concentraiion of CO2 plm & concentra of N2
rangiq from O to 50%. h both caaa, om pham pack-
qe yselds ramlta tbat a4ree weu with publ &til'.
The raulta in column 2 of Tables (4) xd (5) represent
lrztory muea.
Flash caJculations
Tabk (6) shmvs rarults for fimh cak:ulitions on a ten ' b< Repulsion pter & component i in the der
component gystem mex a range of pressuxe which included
the system critical point it 2810 psia and 162.2o!. The
SRK EOS waa used and as expected, the SS method did
not converge near the critAcaJ regmn; hmtever, the robust
MVNR predicted propertSea that a44ree clmely with those
' of Ref. 6. Note thit Ref. 6 usai Powell's methodlo'o
instead of the MVNR. Equally good raiults were obtiined
with other mixtures presented in Rer. 6.
i
i
100-7
W-mW'mm
CONCLUSIONS
The jor contribution ot this work is thit it collects
asid sthemi &ll Worm&iai viW to writing & robust
PVT pe haaal on & generalimd Equition of Stak.
We hive provided uidyticaJ mpremmm for artion of
the partiaJ daimttves used in Newton-Rhapson iteration
for FSve Eqmtions of Sta!e. Procedures for dat
saturatmn pointa (both qper xd kmer) a! a gman ta>
perature hiw been hunestea. F'urtber, on a wxx>
ple method (b on the Succaam SubstitJjaa Fx*>
tion procedure) for whdher tbe gygtem tem-
pme m blxm or bekpw the mxxtme criticaJ tempera-
ture (ut aasan'g iatrri*ts4 tbi er tenpe'r)
were pro'vided. We haw sdau'y sppJ the wu
me axbt wolut prome to sn frve
i Sta&e u i thm wodc-
h HmXuJ. tJa3u pape the &w md
p af & robust commercial qaaJ30 hy
, PVT phaae pa-
ACKNOWLEDGEMENT
Compay for thefi rms suppart duraig tJaxs stw&y. The
authan &!'K) thmk the University d Tum fsx prmidjng
computer fxiutm. "Thffi rmemh w'as performed tmder
the auspmes of the Uniw of Taha Petm Bawflm
Eqktion Projecta (TUPREJo).
NOMENCLATURE
a, Attraction pusme4m m the EOS fz muj-
tiphaae maems* Eq-(4)-
a<,; rule parumtex, Eq.(6).
a<,ffl m7 rule pamnatm, Eq- (B2)- i
A,, Cubic equition coefficient, Eq. (12.1). i
Wmls EOS, Eq.(2).
b<,,, mixing rule pter as defined in Eq. (Bl).
B,, Cubic equation coefficient, F/Q. (12.2).
f<Im Fugacity or component i in phue m.
f<,(, Fugacity of component i in the liquid phase.
fi,v Fugacity ot component i in the or phaw.
i F4 Ratio oF fugacities, Eq. (19.3)
'i

41

'j : k paxamak in the F?dt uid Weraal EOS, %. (A4).

l{
:I
i Componaiti.
?i
K4 K - vaJue of componait i. j Componaitj.
l

L N'amba oT xxxka d uquid per xxx*k d fiuid mature. L Liquidphaae.

Ad Moleculu weight. m phaae.
N. Number & compomnk i & ?ure- miz ?ure.
N4,m Number d mxAea d camponait it phm m.
r Reduced property.
p Sy? prmure, part.
l

aat At mturition point.

I
l
i

p, Critical premure, part

t Trampo*e.
i

p,,< Cri'Ucal prewure of camponent i, part.

i vp At mpor point.
R Un? gas conduit.
V Vipor ph?.
T Sy? temperiture, degree Rankine.
T, Crtt? tpmperatnw degree Rmkine.
Superwcript
T,,< Crit? tempaiture d rowy>'oent i degree Rankine.
* Ideal ? property.
uiim pa? uaad i differen&tm, Eq.(B3).
U paramae in the geneThliwd EOS, Eq.(8.1).
Grsek wtmion
ti- Spacmc molu ?mna 4 phaaa m, ftsllbrruAe.
V Vohu? /ta. a Eqmtffin of State panmekr Eqs. (Al), (A2), (A3).
V Number d molem of mpor per rook d fiuid mxxkty. fi paramete tn the Schmidt - Weuel EOS, Eq. (A6).
;l V, Cr? m?, ft'. 6<4 ?delta..
al
V,,4 0xsti? vobum 4 componmt i, /ta. r Futd? defined i Eq. (19.5)
l

w4,, pa? umd in d3ffetentia!joas Eq- (a4)- w ? fxtor.

W '?tm tn tb=e geaer? FiOS, Eq. (8.2).
z< Mok 'fraction d ?t it the l?d phaae.
%iim Mok fraction d romponent i m ph? m.
y< Mok frxtion of romponait i m the vapor phaae.
l)i 4 0verall rook frxtm d compo'?t.
!'I
n mi de W? co&c?, Bqa. (1), (2).
i<,, Fu?ity coeffic?t of componait i in phaae m, Eq.
(21.1).
p Denaay,Ikruie/fta.
q paxsmeter in the ?t - Weml EOS, Eq. (A8).

Z Compresmibility factor.
{! REFERENCES
Zm Compmmibility fxtor d phaae m.
Z: Compremibility factor of component i mttirated liquid 1. Redlmh, 0. amd Kwong, J.N.S.:'On the Th?ody-
' 7"aat,i uld T. namiai of Solutions. V - An Bquiticn of State. Fu-
Z<,y Compremibility fxtor of the liquid phaae or compo- gacitiai oT Gaaeotm Solutiom,' Chemical Reuiew, Vol.
nent i. 44 (52-&3).
2. Zudkevitch, D. amd Joffe, J.:'Corre!ation asd pre-
Subscripts dic'Uon d Vapor-Liquid Equilibria with the Redlich-
a Relit#e to the pasameter a.
Kwong Equation of State,' A}ChE Journaa, Jan. 1970,
(112-119).
b Relatm to the pazuneter b.
3. Soave, G.:'Equuibrium Constants from a Modified
c Critical property-
Redlmh-Kwong Equation of State,' Chemical Eng'i-
deui At dew point.
neering Science, 1(;}72, VOI. 27, (1197-1203).

*oo-s
, .@-, ,4 ,;,% - ,}p !; ,!y , -f>4> }rL %V- :;+ 4rm;2-=%?.s::&>ss-ys-71.?T,z-Trs;-1-r"al'h%T"s9fiff*'sa!lv&#tr%! >,
QP'
"W
4. Peng, Ding-Yu and Robinson, D.B.:'A New Two -
Constant Equition of State,' IruL Eng. Chem. Fund.
(1976) 59-64.
5. Schmidt, G. uid Wemel, H.:'A Modified Van Der
I
Wmls Type Equa!ion of Skte,' C7iem. Eng. Science,
i
VOI. 35, 15€)3-1512.
l
6. Nghiem, L.X., Axm, K. uid Lt, Y.K.:"A Robust Iter-
ative Method for Flash Calculations U the Soave-
i
Redlich-Kwong or the Pez4-Robinson Equation of
Stite,' SPEJ, June 1983, !521-530.
7. Fussell, D.D. md Yamasik, J.L.:'An Iterative Sequence
for phase-Equuibria Calculationa Incorporating the
Redlmh-Kwong Equation or State,' SPEJ, June 1978,
173-182.
8. Lohrem, J., Bray, B.G. and Clark, C.R.:'CaJculating
Vmmities of Raservoir Fluids From Their Compos;
tions,' JPT, Oct. 1964, 1171-1176.
9. Jcmi, J.A., Stiel, L.L and Thodm, G.:'The Viscosity
of pure Substanca in the Dense Cm and Liquid
phum,' AIChE JournaJ, Ma 1962, Vol. 8, No. 1,
59-62.
10. Heraing, F. and Zipperer, L. :' Calculation of the Vm-
coaity of Tecal Gas Matura from the Vu<osity of
IndividuaJ Gaaal' Gu u. Wwaerf, (1936) 79, No.
:ig, eg.
11. Stiel, L. I. and T$odos, Georgei:' The Yuscoaity of
i Nonpolar Ga at NormaJ preasure,' AICHE J., (1962)
8, 59.
12. Modell, M. and Reid, R.: Thermodynamicm and
l
' Sts applicatiom, Prentice Hall (2ed.)i Prentice Hall,
Inc. (1983), pp. 151, 189.
l 13. Reid, R.C., Prausnitz, J.M. and Sherwood, T.K.: The
proptrtiu o/ Caau and Liquida, 3rd Edition Mc-Graivt
Hill }977 New -York.
I 14. Wilson, G.:"A Modified Redlich-Kwong Equation of
Statm, Application to General physical Data Cilcula-
tions,' pzper 15C presented at the 1968 AIChE Na-
tional Meeting, Cleveland, OH, May 4-7.
15. Baker, Lee E. and Luks, K. D., :" Critical point and
Saturation pressme CaJculations for Multipoint sys-
tems,' SPEJ 1980, 15-24.
16. Coats, Keith H.: An Equation or State Compositional
Model,' SPEJ, October IG)80, 363-376.
100-9
17. Firoombadi, Abbas : Rmervoir - Fluid phaae Be-
hy5or uid Volumetric prediction With Equation of
Stite., JPT, April 1988, 397-406.
18. Hong, C.: 'Lumped-C'omponent Characterixition or
Crude Oils for Compositiond Simuldionl' SPE DOE
106')1 241-245
19. Powell, M. J. D.:"A Hybrid Method for Non}ineas
Eqmtiona,' Numerical Methodm for Noear
klgebraic Equatlonsi, T. Rabinowitx (ed.), Gordon
and Breach, London (1970).
20. Powdl, M. J. D.:'A Fortrm Subroutine far Solving
Sygtems of Nonlinear Algebraic Equitions,' Numer-
ical Methoda for Nonlinear Alpbr Equa-
tionm, T. Rabinowitx (ed.), Gordon uid Bre, Lon-
don (1970).
21. Yarborough, Lyman: 'Appucationa d A Genexsli
' Equation Of State to Petroleum Fluid4' m: Eqtsa-
tioru Of State in Eninaering, Advarseei in Chtmixtry
Seriea, 182 K. C. Chao md Robert L. Robimxn, ed.,
Ame=ricy Chemical Society, Wamington, DC, (]J79),
385-435.
APPENDDC A
EOS PARAMETERS
Here we present acpressiona for the parameters a, n@
and n6 for the EOS'a discumed m thLi work.
Redlich Kwon EOS
The function a * given by
1
a
with = -, (.41)
8
$1@ = 0.4274802327
asid
11, = 0.08664035
Zudkevitdi Joffe Redlich Kwon EOS
The function a is the same as Eq.(Al). Zudkevitch
and Joffe developed a method of computing n,,< and n63
for each component i at a given temperiture using the com-
ponent's mpor premure, aaturated liquid density and Ly-
ckman's fugacity coefficient14. An extensive application of
the RK EOS to reservoir fluids was ma4e by Yarborough 2 '.
He used the Zudkevitch - Joffe RK EOS (ZJRK) with tla,<
and n6,; as functions of reduced temperature and acentric .
 l

i factorl2 md with binu7 intenctmn parameter developed ' is mj'ved for 04. u m iterdive method (such u Newton -
ror the caaes i hand.
', Riphaon) u uaed to wkve this cubic, then ui initisil pma
Soave Redlich Kwo EOS
is provided vic
Ha'e a ia given by: '
flc,< = OJS989 - 0.O]217w4 + 0.(Jm't&wi'. (A7)
' a = 1 + (0.48SO8 + l.5Sl71v - 0.1561:%i2) (1 - ) 2
(A2) The tmal!mt root ot Eq. (A6) is uaed to compute an
: intemed3sry puauneter le,< as fouowsi:
i

where T, = TIT,.
Here, n, and !l> sm the suna u tot the RK EOS
.1
Pe Robinson PR
ee,i=
3 (1 + fielt'Ji)
. (as)
hi c:

Finally, n@,< and n6,6 g#en by the follow% ex-

a = 1 + (0.37464 + l.S422&.i - 0.26GK)2u2) (1 - 1/3) 2 preasionm :
(,43) , na,< ""' 11 - ec,i (1 - fia,4}la ; (A9)
. with
and
, n@=0.45724
and
' (lk,i'afia,tec,i- p410) i
€W- n, = 0.CK)778 APPENDIX B l
Schmidt Waml
EVALUATiON OF PARTIAL DERJVATrVES
The fanction a i given by
=s We prmant the dertvat#a or the partial fugacitia
' with reqect to the vaxioua variffiles for ewh iteraUon. We
a = 1+&(1-) 2; T<T, (A4) ' wul perfom the diffamtiition on the gener fugacity
l

s?
iW
where equation
with thait spplim
the ippropriate to all prmnted Equationi of Stite
parameterm.
l

F dduie the following, -

€ kss Uw<;0.4;
l.-!l
&, k2, U w 2 0.55; btaim %= ....bt %= ....1 nb,iT"Te,i, ()
i'
(§) k2 + W) k1; othawiae bm Bm TPe,<

r
Ji,

l
with
k, = i (r170/
ko=s O.465
0.71 +(T,
+0.5361 S.347w - 0.52&y2;
/llf w S z
- 0.779)' O.3671;
ks=ko+t-1(s",-s&,,-i) (82)
ui,m
where m'a
A,, bi,m
= Liquid
'ai" a L l=l
'- 2ai,m
or Vzpor;
zl-mP/na,ina,Ia<al
N,
(1 a kia) V,,42m (J'(Te,<Tc,l)
r
ei J'eil) 7y@
B,,n
llxi ? i + 0.'9S93ui if w > 0.3671
3(U + 2) b',' (W, - t,g)
:n
a = 1.0
Here
and T, *- the
(0.4774 + 1.32&-i)
reduced ln Tt;
temperature andT w> isTe.
the(45)
scentric
[
factor of the component considered.
+ 52 I k ' xNa zh , 6 :- 7 ( B 3 )
ia-!l

% - - 4 W L"'iim
k ' 1" x="
k (, Bm
61-E -S7 3 ('i
) -u2
W) b'!"
II

+
l-.
The method used by Schmidt and Wetvela to emluate 1
'
hu
:ffi naii (w,) and n6,;(u<) is now deacrSbea. For each g;ven l x ('2Zffl + UZm + 2WBm + UBm) (84)
l

value of w,, the cubic

2i + 1) fi c31i + 3fic2,i + 3fic,t-1 = 0 (xe)
- :x or - iteration
J
l

I?

'k'

100-10
sbes;?"A-a7:;",:"'@?'a' ?m> =imaw"%"
,' { ::a' @ -'l"{-q?;'%yt,-4,
; 'a i 'i"" 4" '-' it Q'W'a" lz" Axoi
?'&?'tkw
fi-:,"W'7. =":
mtsvv 11
[?la'aafl!ii3
'€-"'-?"" "? """"'-':"ie="i?
-4

i
We wul develop the daivatm of the p?id fugacity
A[-(Th)]=
i
I
i

with mq>ect to presmure for component i m ph? m.

a/i,m ( 1 apaps t
? aft,m < -
ap ip zz,, + u:a,. + n,,?
g 18 '
apaps t. (Bll)
-6[-=-(Th)] 2%,, + un,,, - n,,,? '

aw4,ffl l (35)
+ ? l s
ap 1 ay,,. n,?a<yln,.). (812)
-"'- 'a *,ws {
?
A-n
0'!?
" aa'll1l'l -
Am h
where,
a az,,
(B6)
ap ap
a (A,IB,,) . ?1 ?aA,, - ?A,,, ?aB.., (Blj)
rod ?-8,, 8p n,' %
aZ,,, aZ,,aA,aZ,,,aB,,
8p aAm ap ' aBm ap -ThDh- --

Diffantiatitiy the cubic equatmn with rwpect to A,, aA, - A., (m4)
?:%*- '?? '?m a'
and B,, we yet

aB,, B.
aZ,, = (B- - &) * (B8) #
M
o, #, (815)
ay Y' 'l

Note tbm the foumaag eqmtiaas vmM be needa! mJq

asid
az,, x' for the SW EOS wum w4 - w = O for tbe other cwaa.
?svs'-'a'a '?spa l P)
aB, Y@
awi,
%i%lii,?
1 a
where
-ap' (z,,-n.}2%
X' . Z,z (1- U) - (2fi,, - 2UB, - U) 2,
+ (wn,,2 + w& + b),
-[?=ffi61
x (z!- + UZm + zWBffl + UB,,,)
and
-[(-.-.-.) ?=-!..S]
Y' = 3Z,,,' - 2 (3,, + 1- [78-) Z,, r az,, aBml
(B16)
+ (WB',, - UB,,' - UB,, + Affi).
All the equatxnsi derived zbme ddine the vairiatffin
Note that U and W ? functmns of composition rod
i
of the p?ial fugaeity of both phaaa with rarpect to pres-
not of presgure so that they ue not aHec? by this differ-
atire, whd appears in the Jxobian mitricei of both the i
entiation procms.
p - z rod the p - y iteratioas. The partial derivdive of
the psxtiaJ fugacity of mpor wtth reapect to the gas mole
A [- (Th)] = fraction composition which ippem in the p - z iteratmn
Jacobiui is the aame as the one dewloped below for the

l-l,. 2%,,, + un,, - n,? )]

"' ap[-(
a l,. / 22,, + un,, + ri,,,?
's,?TM L - :x iterition.

L - % iteration

100-11
f
 ':W'M"i"#!'?h'fflamm

af"' a fi,V 64,z + lbilV (J7V a 1))

aVi Vi aMi
sa RecaJung thit U = 1 + :Sw, uid thd

sa :'i"-al wizi,mbo; a'

l
!
-a : (zv - Bv) """ ao zN,.1 zi,mb2aT a
a 2Zv + UBy + Bv then
"aMj "'v ' 2Zy % UBy - Byn
a[J bjo' ('j Zi";i Vtb" " aaa Si':"l '<V<bo< a') '
I

ayi
aw<Iy -=3 .
+-i(fll7)
a azy aV3 (J21]jt*l yt6ql.7)a
(mS)
(818) ayj lbi,v (jv - 1)l = - (Zv - 1) bi,v%,v + bi,v ,, ; Again, we hzve aw au
where - = --, (826)
ayi ay3
ab,,
' "a -bi,v%,va
i %sZy i(8F))
Here s function of Ay, By, U uid W, wbj& in turn
am all functffina of the compmkion. Thus
'aaVi
a
uilmln
2Zy 2Zy + UBy -+ By
+ UBv By
a
l

ay; aAv ayi aBv av4 aU % aW av6

-aZy=aZv
(B'XJ)
- -aAv+aZy- -- aBv + aZv-aU - aZv
+ -aW- 2Zy + UBv + Bv
' %; 2ZV-By
"im ln
+ UBy - ny
mpect"'rv7y.- n&,51ei
....aBv
azy azy
sund a-v &!1aigiv(B21)
en by Eqa.(B8) uid (B9) re- . +ln -!-i (m7)
2Zy*UBv
2Zy+UBy+Bv asi5 au<-

ast3 Tpe4 -ln

a :zzy
aMj 2Zy++ uny
UBy+- By
Bv :
i -,1 2-azvY + av3
{[7 + l')iByj
-aB'
W-
(m2)
i .ahA,v += 2,Il%l yi (1 = kjl ) V aa.;na(p,la:paci,€)Te) Te,i) ;
x, !

Now, the follotving exprsaioni ue m0 nsmded tox the

i

+Bv +
aU U%F-2T;"aW
l
I

i i
it
11 %i
azv
SW = uexobtained
EOS. They . (m," from the cubic equation
}
l?!

i a aU
%i
i a,u
+Bv ayyl
- tr W, , z!.F layH
-2;-az'
Y"
+ ( u + S -aB'
!ii
! l
where '
vthm
(ms)
i X"uid
: -BV:?'r + (2Bv' + BV') Zsr - (83 + 83) i Y = 2Zy + UBy + By.
1
H+' X" = 323 - 2 (By + 1- UBv) Zv Finally, To euate -'- amd -, we will need to
aSli aMi
, at5y aw<,v -
l:
+ (WB2v - UBv2 - UBy + av). apply the product rule to the aerivztSves oF the parameters
ij
d Since U + W = 1 (see Eqs.(8.1) and(8.2)l then developed uid to the rollowing,
,a%,, 1 aA,
azy azv
-=--(m4)
- -a',V -
aw au
ag, Ay ay,

+ (1 = A:l,,.) ffl(pellpc,)7'n.(B29' )
?.l
.1;

J
l;,'?i

i.;j

100-12
 wp
.a..%:?:I"%.::'
':"' o " ::?a"a"'aY"" Z' "-" - a--" J 'a:"' "" ' -"""'a""""""!s,' 13%,,2
e' B % J'>"> -,[4e "!'-4?J?.:
%'oe':r%? 6
?Sc.l ': {1,la,a=":'1'lffi. tnt ]
-*

All these expremiona allow us to find 'jX-yj for the

I.
I
l
L - z and the p - y iterations. now we wul emuate 'jA
az6
'e=*[-=-gl
'j
needed for the L - z and the p - z iterations. We remind
I
the reader tbat here the z3 is one of the iterition ?iablm
?A1,I
Az,
(1 = k1j) 1 /n@4n@<pl:spc,;
gal a; €Te,s
) ra
TcJJ'
l and thus the differentiation * alightly different. €k,z. aAc
Az az3 ' (835)

All thme expremions do aipp}y to the V - y iteratian,

.?aaf:,$1, %= /m0,L (. Zlj(4-.,1: f , s, ; U providai we replace V by L, zz by y5 uid ?vemi.
a xg
7z, [b<,L (7v - 1)]- zv - Bv ;z, (Zv - Bv)
-,,, [- (ff)]
a'3
'i,L
+-'-'-
a% ) (m)

The di&rpntiatiou proceu of the eqtuitian above %

emct% the aame u for-aut,V
F-!!!-,., 'except for the following-mod-
ifications due to the fact thit z4 iei am itea!ion vu'iabie:

abi,
?hj" o bt,Vbl,V o b<,V%,V- (flsi)

The deviationfytoas 4aiv4tjva ag the rome aa thme

er?uated aJ?e. -, -, - uid - aze modified
'-&8
az3 az; ar-4 az;
aBL nbjpTei nbJPTei,
azj ' "T'ei '?Tpe3 -' (fl32)

aA,
?"a':*L €-[-=-81
.21 z, I(1
;. ='Lizi
I

J H???s

-€-l-4,}
(flss)

aU ( (w5bjo' - w,y,o.v)
-=3<
az4 ( (X"- rsb9-71
,-l-1 € ,
a

(60, - 7 ? 6 ? - 7 ) X l,??l"a w t' z 1. 6 ? - 7

}
l

/ 12' I (Js<)
(Il".41 zl,5?.7 )
i
I

& 100-13
a
4'4 :JC-':';?, ;ss'aroa' s - r, Tff,,:% o-i*'- s";-r'w4 l ts:sy-g +t-%lh; z{ ss . -s(xwH 7! 6, yWsvwsa?,,;;r t') fflf?'a'a',,-":Y7Jla'a,,,.

TABLE l

Compumn of calcul? uid exp?mkd tssha fs tha Cl / it - C4/ !1 - CIO

Zudk?tch - Jof* - R? - K'mmg EO8

!
("F) L 'Lffi,l
F'remux* (paia)
[ € 'Lib. g[
K-Vdtie l
i
1000 i 1019.7 995 3.813 3,773 ' 3.736
o.eis ' 0.637 o.asa
l
0.032 o.osi 0.a32
20001 1970.5 1912 1.861 1.867 1.850
o.eos , 0.613 0.629
j

0.122 0.099 o.ios

30001 M.6 2915 . 1.4!i9 1.473 1.470
l

0.631

10001
0.635 0.645
o.i'es i 0.156 0.157
972.1

0167 l
l
976 3.174
0.297 3.173 3.173

20001 1950.9 1960

0.013
i.as<

0.039 l
o.nr
o.oos
1.862
0.297
i o.ooa
i i.sei
o.sai ' 0.3a
l

1.213 , 0.028 l O.028

j

10.221
3000 3121.2 3143 0.703 l 1.254 1-252
0.$30 0.63S o.asa
l

o.'tsa

TABIE 2

{xmpsx?ti of cdc? rod axperimaiul rw'ahs fm th* ci / ii- C4 / it - C16

Pen( - Rob? EO51

T 4 Prs*a (paii) K-Vahe i

(oF) JW Q rPada(* i
'.

2W 0.203 1000 1009 1009 3113 3.aKX) 3.800"

0.346
o.sss 0.615 o.eis
0.451
o.osz o.oss o.ms
2%) 0.402 2000 1940 1941 1.M!1 1.&44 1.844
0.370
0.605 0.625 0.625
o.za
?).122 o.iig . 0.119
2K) 0.575 3000 2999 3000 1.459 1.460 1.462
0.179
0.631 0.639 0.639
0.246
o.sgs o.sao 0-181
160 0.253 10a) 952 954 3.l'l4 3.130 3.126
0.661
0.297 0.313 0.315
o.oaa
0.013 0.(XX} 0.009
160 0.459 2000 1937 1940 1.854 1.850 1.848
0.390
0.367 0.374 0.376
0.151
o.osg 0.034 0.034
160 o.eas 3000 3113 m7 1.213 1.247 1.245
0.229
0.703 0.643 o.ua
o. ios
0.330 0.241 0.244

100-14
 l

TABLE 3

Comparffim of cakW atid ?y - ---#

'til n tilt far lk* Ci/ n - C4/ a - C16
?t - Wmml DO51

T $4 F%wa (pmm) K-Vah*

('F) Lab. W 'L*. '

'
280 o.m 1000 1012 1012 mJl3 -' $150 :l.ml -
o.sa o.sts OJ!l? o.u"t
041 o.m a o.m
280 0.402 2000 1927 1928 ljell lJ73 l.l7$
0.370 o.aos o.aoo o.m
0.221 oan o.ioo a.109
280 0.873 3000 295!! 2%? 1.4$9 L4?'l l.4Th
l

0.179 o.ui a.a o.m

0.246 a.la!l a.16!i 0.IW
160 0.253 1000 Wl ' W2 ' 1174 $.l&i S.kS2
o.mi 037 03)4 o'.sos
0.Oa6 a!lu , 0.001 i 0.007
l

160 0.459 2Ca) 1940 W 1J&4 1.W7 LaW

a.S90 aJl7 o.ui 0157
0.151 '( ' 0.OW ' om
160 o.eu 30m 310!& $1% 1331 L2u 1361
0.229 0.70a o.eii o.at<
0.101 p ossx o.m

rwrs 4
C? d '? P? &r C(% / Cl - C,
P? - Rob?. EO8
-

"- ca"'m' i'i:i "-h'

BmbN* Pomt
(m
wkJi O% CO-, ssx 1139
20% 16 lJUi7
40% ffl ffl
60% 22! 2234
66% W 2)a30

Dm P
€paffi)
l

with a)% C(% 2113 2110

65% 240? 2406
70% s*aa 2866
75% 3182 3179 '
80% 378 sm

:
l 100-15