Module Cubic EOS and Their Behavior

Module Cubic EOS and Their Behavior (II)
(Modified 26 Aug 2008)

Module Goals
Module Goal: To demonstrate thermodynamic quantification using modern cubic EOS
Module Objective: To high!ight the most often used cubic EOS
Module Introduction and Purpose
Introduction
The basic essence of engineering is to harness the tremendous energy of the uni"erse# in its !atent or $otent
form# to reso!"e socio%economic $rob!ems Most often than not in the $rocess# energy must be con"erted
from its natura! form into a form that is more amenab!e to human uti!i&ation 'etro!eum and natura! gas
engineering is no different (t is a disci$!ine focused on efficient!y e)tracting the $etro!eum buried dee$ *ithin
the earth and getting it to *here it is needed The $etro!eum f!uids of $articu!ar interest to the $etro!eum and
natura! gas engineers are crude oi! and natura! gas The term crude oil is used broad!y here as to
encom$ass the different forms of $etro!eum !iquids that are used for energy and other $ur$oses
+atura! gas and crude oi! are natura!!y occurring hydrocarbon mi)tures, genera!!y they are referred to as
petroleum fluids These f!uids are found underground at e!e"ated $ressure and tem$erature conditions
'etro!eum f!uids are com$osed $rinci$a!!y of hydrocarbons, "arious non%hydrocarbon com$onents# such as
nitrogen# carbon dio)ide# and hydrogen su!fide# may a!so be $resent
'roducing# se$arating# trans$orting# and storing $etro!eum f!uids are the $rimary res$onsibi!ities of a
$etro!eum and natura! gas engineer Therefore# *e ma-e no mista-e *hen *e refer to natura! gas and
$etro!eum engineers as petroleum fluid engineers These engineers dea! *ith hydrocarbon f!uids to ma-e a
!i"ing As a consequence# they may "ery *e!! be referred to as hydrocarbon fluid engineers. One cannot
o"erem$hasi&e the im$ortance of the $rimary f!uids . oi! and natura! gas . to the modern industria!
society (ndeed# modern man/s re!iance u$on natura! gas and crude oi! as the $rimary source of energy is
such that these f!uids are abso!ute!y critica! to the o$eration of today/s industria! society (t is fair to assume
that you# the reader# are interested in hydrocarbon f!uids $roduction
At e"ery stage of the $etro!eum e)$!oration and $roduction business# a hydrocarbon f!uid engineer is
needed 0ydrocarbon f!uid engineers might find themse!"es dea!ing *ith acti"ities such as reser"e
e"a!uations# dri!!ing o$erations# reser"oir ana!yses# $roduction o$erations# and gas $rocessing They are#
therefore# ca!!ed u$on to dea! *ith a *ide s$ectrum of acti"ities# most!y dea!ing *ith f!uid hand!ing and the
associated faci!ities
Most of the f!uid hand!ing $rotoco!s require the engineer to -no* a priori ho* the f!uids *i!! beha"e under a
*ide range of $ressure and tem$erature conditions# $articu!ar!y in terms of their "o!umetric and
thermo$hysica! $ro$erties 1or e)am$!e# the engineers shou!d -no* if the reser"oir contains a dry gas# a *et
gas# or a gas%condensate before they design the surface $roduction faci!ity This is co!!ecti"e!y termed fluid
phase behavior (t is therefore# not an o"erstatement to say that a thorough understanding of hydrocarbon
fluid phase behavior is essentia! for the *or- of a $etro!eum and natura! gas engineer 'hase beha"ior has
defining im$!ications in $etro!eum and natura! gas engineering $rocesses 'ressure# "o!ume# and
tem$erature ('2T) re!ations are required in simu!ating reser"oirs# e"a!uating reser"es# forecasting
$roduction# designing $roduction faci!ities# and designing gathering and trans$ortation systems
En route from a subsurface reser"oir to man/s energy e)tracting combustion $rocesses# a hydrocarbon
mo!ecu!e goes through "arious $hase% and $ro$erty%a!tering intermediate stages These $ro$erties are
crucia! in designing and o$erating the $rocesses efficient!y and o$tima!!y 'hase beha"ior thermodynamics
gi"es us the too!s needed for gaining the desired understanding of how fluids behave at any of those stages
Questions? (f you ha"e questions at any time during this !esson# $!ease fee! free to $ost them to the
Course Introduction Discussion Forum (3!ic- on the Communicate tab in A+4E5 to
access our course discussion forums)
Why Study Phase Behavior?
+atura! gas and crude oi! are natura!!y occurring hydrocarbon mi)tures that are found underground and at
e!e"ated conditions of $ressure and tem$erature They are genera!!y referred to as $etro!eum f!uids
'etro!eum f!uids are $rinci$a!!y made u$ of hydrocarbons, but fe* non%hydrocarbon com$onents may be
$resent such as nitrogen# carbon dio)ide and hydrogen su!fide
6e ma-e no mista-e *hen *e refer to +atura! 4as and 'etro!eum Engineers as 1!uid Engineers This is#
engineers that dea! *ith f!uids to ma-e a !i"ing Moreo"er# *e s$ecia!i&e in t*o s$ecia! f!uids *hose
im$ortance to the society cannot be o"erstated%%indeed# human-ind re!y on natura! gas and crude oi! as the
$remier source of energy that -ee$s the society o$erati"e As a consequence# *e may "ery *e!! be tit!ed as
0ydrocarbon 1!uid Engineers That is e"erything *e are basica!!y about At e"ery stage of the oi! business# a
0ydrocarbon 1!uid engineer is required This is# reser"oir ana!yses# dri!!ing o$eration# $roduction o$eration#
$rocessing# among others# re"ea! the *ide s$ectrum of areas *here an engineer *ith e)$ertise on
hydrocarbon f!uids is fundamenta!
This being said# *hat can be more im$ortant for a 0ydrocarbon 1!uid Engineer than understanding ho*
these f!uids beha"e7
(t is not an o"erstatement to say that a through understanding of hydrocarbon $hase beha"ior is
quintessentia! for the 'etro!eum and +atura! 4as Engineer 'hase 8eha"ior has many im$!ications in natura!
gas and $etro!eum engineering 'ressure# "o!ume# tem$erature ('2T) re!ations are required in simu!ating
reser"oirs# e"a!uating reser"es# forecasting $roduction# designing $roduction faci!ities and designing
gathering and trans$ortation systems
E"ery hydrocarbon mo!ecu!e in the reser"oir is to embar- on a fascinating 9ourney from beneath the earth#
$assing through a great dea! of intermediate stages# to be fina!!y dum$ed into our atmos$here u$on
combustion (re!ease of energy) 'hase 8eha"ior is the $art of thermodynamics that gi"es us the too!s for the
com$!ete understanding of ho* f!uids beha"e at any of those stages 5et us be the *itnesses of this e)citing
9ourney
Summary
:egard!ess of the as$ect of $etro!eum e)traction $rocess . be it dri!!ing# reser"e estimation# reser"oir
$erformance ana!ysis# reser"oir simu!ation# tubing f!o* hydrau!ics# gathering design# gas%!iquid se$aration#
oi! and gas transmission# oi! and gas metering or qua!ity contro! . a good $redicti"e -no*!edge of $hase
beha"ior is ca!!ed for This course *i!! he!$ you to acquire this -no*!edge ;ou may ne"er ha"e to de"e!o$
com$uter routines for doing many of the $redicti"e ca!cu!ations $ertaining to hydrocarbon f!uid $hase
beha"ior, ne"erthe!ess# the -no*!edge base de"e!o$ed in this course *i!! he!$ you de"e!o$ the
understanding needed to be an inte!!igent user of commercia! soft*are $ac-ages and as- the right questions
that your res$onsibi!ity as an engineer demands
Action Item
6rite a $aragra$h or t*o describing# "ery brief!y# your educationa! bac-ground and $ractica! e)$erience#
inc!uding your -no*!edge of $hase beha"ior (if any) and ho* you a$$!y or ha"e a$$!ied this sub9ect matter in
your current or recent *or- assignments 'ost your $aragra$h(s) to the Modu!e < Message 8oard in our
on!ine course en"ironment (A+4E5 . htt$=>>cms$suedu>) 1rom our A+4E5 course en"ironment# c!ic- on
the In Touch tab
Scro!! do*n to the ?Message 8oards? section# then c!ic- on the !in- for Module 1 Message
Board
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in another a$$!ication
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fe!!o* c!assmates
Multiple Roots and Cubic Behavior
(t comes as no sur$rise that cubic equations of state yie!d three different roots for "o!ume and
com$ressibi!ity factor This is sim$!y because they are a!gebraic equations# and any n
th
order a!gebraic
equation *i!! a!*ays yie!d @nA roots 0o*e"er# those @nA roots are not required to be distinct# and that is not
a!!= they are not required be rea! numbers# either A quadratic e)$ression (n B 2) may ha"e &ero rea! roots
(eg# )
2
C < B 0), this is because those roots are com$!e) numbers (n the case of cubic e)$ressions (n B D)#
*e *i!! either ha"e one or three real roots, this is because com$!e) roots a!*ays sho* u$ in $airs (ie# once
you ha"e a com$!e) root# its con9ugate must a!so be a so!ution) (n our case# and because *e are dea!ing
*ith $hysica! quantities (densities# "o!umes# com$ressibi!ity factors)# on!y rea! roots are of interest More
s$ecifica!!y# *e !oo- for rea!# $ositi"e roots such that in the case of mo!ar "o!ume and in
the case of com$ressibi!ity factor
(n a cubic equation of state# the $ossibi!ity of three rea! roots is restricted to the case of sub%critica!
conditions (T E Tc)# because the S%sha$ed beha"ior# *hich re$resents the "a$or%!iquid transition# ta-es $!ace
on!y at tem$eratures be!o* critica! This restriction is mathematica!!y im$osed by the critica!ity conditions
Any*here e!se# beyond the S%sha$ed cur"e# *e *i!! on!y get one rea! root of the ty$e 1igure <0<
i!!ustrates this $oint
Figure 10.1: Multiple Roots in Cubic EO
5et us e)amine the three cases $resented in 1igure <0<=
< upercritical isot!er"s #$ % $c&: At tem$eratures beyond critica!# the cubic equation *i!! ha"e on!y
one rea! root (the other t*o are imaginary com$!e) con9ugates) (n this case# there is no ambiguity
in the assignment of the "o!ume root since *e ha"e sing!e%$hase conditions The occurrence of a
unique rea! root remains "a!id at any $ressure= any hori&onta! (isobaric) !ine cuts the su$ercritica!
isotherm 9ust once in 1igure <0<
2 Critical isot!er" #$ ' $c&: At the critica! $oint (' B 'c)# "a$or and !iquid $ro$erties are the same
3onsequent!y# the cubic equation $redicts three rea! and equa! roots at this s$ecia! and $articu!ar
$oint 0o*e"er# for any other $ressure a!ong the critica! isotherm (' E 'c or ' F 'c#) the cubic
equation gi"es a unique rea! root *ith t*o com$!e) con9ugates
D ubcritical isot!er" #$ ( $c&: 'redictions for $ressures *ithin the $ressure range for metastabi!ity
('A/ E ' E '8/) or for the saturation condition (' B '
sat
) *i!! a!*ays yie!d three rea!# different roots (n
fact# this is the on!y region in 1igure <0< *here an isobar cuts the same isotherm more than once
The sma!!est root is ta-en as the s$ecific "o!ume of the !iquid $hase, the !argest is the s$ecific
"o!ume of the "a$or $hase, the intermediate root is not com$uted as it is $hysica!!y meaning!ess
0o*e"er# do not get carried a*ay Subcritica! conditions *i!! not a!*ays yie!d three rea! roots of the
ty$e (f the $ressure is higher than the ma)imum of the S%sha$ed cur"e# '8# *e *i!! on!y
ha"e one (!iquid) rea! root that satisfies 8y the same to-en# $ressures bet*een 0 E ' E 'A/
yie!d on!y one ("a$or) root (n the case of 'A/ being a negati"e number# three rea! roots are to be
found e"en for "ery !o* $ressures *hen the idea! gas !a* a$$!ies This can be seen in 1igure <0<
as *e!! The !argest root is a!*ays the correct choice for the gas $hase mo!ar "o!ume of $ure
com$onents
Most of these considerations a$$!y to the cubic equation of state in G (com$ressibi!ity factor) The most
common gra$hica! re$resentation of com$ressibi!ity factor is the *e!!%-no*n chart of Standing and Hat&#
*here G is $!otted against $ressure Standing and Hat& $resented their chart for the com$ressibi!ity factor
(G) of s*eet natura! gases in <IJ2 This chart *as based on e)$erimenta! data 4ra$hica! determination of
$ro$erties *as *ides$read unti! the ad"ent of com$uters# and thus the Standing and Hat& G%chart became
"ery $o$u!ar in the natura! gas industry Ty$ica! Standing and Hat& charts are gi"en for high tem$erature
conditions (T F Tc or Tr F <) 1igure <02# using a cubic equation of state for a $ure gas# $resents the
qua!itati"e beha"ior of the so!ution of G "ersus $ressure (sotherms (T F Tc) sho* the ty$ica! qua!itati"e
beha"ior *e are accustomed to seeing in the Standing and Hat& chart 3ases T E Tc (Tr E <) are not as
fami!iar to us# as they *ere not considered by Standing and Hat& 1or such isotherms# it is c!ear that you
come u$ *ith t*o "a!ues of G (!iquid# gas) at saturation conditions
Figure 10.): Co"pressibilit* Factor versus +ressure
Modern Cubic ES
At this $oint# *e ha"e a cou$!e of comments on the cubic beha"ior that the $ioneer *or- of "d6 introduced
to the fie!d of equations of state 1irst# *e can say that the "d6 cubic beha"ior is qualitatively reasonab!e,
and second# *e can say that it is ca$ab!e of describing the continuity bet*een !iquid and "a$or
+e"erthe!ess# "d6 cubic EOS has been $ro"en not to be quantitatively suitab!e for most engineering
$ur$oses 3ertain!y# it yie!ds unacce$tab!e errors for the quantitati"e $rediction of densities and any other
re!ated thermodynamic $ro$erty 0o*e"er# a!! of the de"e!o$ment in the fie!d of $hase beha"ior that has
been achie"ed today is due to the *or- of "an der 6aa!s A!though his o*n equation is se!dom used
because of its !ac- of accuracy# his $rinci$!es are sti!! the foundations of the current de"e!o$ments "d6
conce$ts *ere so far reaching that he *on the +obe! 'ri&e for his equation
The truth is that "an der 6aa!s/ accom$!ishment in <8KD triggered a tremendous effort among scientists to
ma-e modifications to his EOS *hich *ou!d remo"e from it !arge disagreements *ith e)$erimenta! data
This effort has not yet ceased today and is not !i-e!y to sto$ in the near future Much of this endea"or has
focused on ho* to better mode! the attracti"e $arameter @aA and the re$u!si"e term @bA# *ith the ho$e that *e
can get better quantitative $redictions +atura!!y# the qualitative cubic%nature of "d6/s origina! EOS is a!*ays
$reser"ed# and hence a!! subsequent refinements be!ong to the same fami!y of modified%"an%der%6aa!s
equations of state 6e refer to "d6 EOS and a!! its descendents as cubic equations of state# because# as
*e ha"e said# they ta-e a cubic form *hen e)$ressed in terms of "o!ume or com$ressibi!ity factor and are
e)$!icit in $ressure
(t is fair to c!aim that modern cubic EOS started to ma-e a difference *hen a tem$erature de$endency *as
introduced to the attracti"e $arameter @aA (nteresting!y enough# "an der 6aa!s *as con"inced that the
$arameters @aA (and e"en @bA) of his equation of state *ere not necessari!y constants and suggested that#
indeed# some de$endency on tem$erature cou!d be found A "ery interesting discussion on this# from "an
der 6aa!s himse!f# is found in the !ecture s$eech that he offered during his acce$tance of the +obe! 'ri&e in
'hysics# in <I<0# for his *or- on the continuity of "a$or and !iquid This s$eech and the biogra$hy of this
great $hysicist# Lohannes Mideri- "an der 6aa!s (<8DK%<I2D)# can be found in the *eb resources of the
+obe! 'ri&e organi&ation
The most $o$u!ar cubic EOS# *hich time has $ro"en to be most re!iab!e# are=
:ed!ich%H*ong EOS#
Soa"e%:ed!ich%H*ong EOS ("ery $o$u!ar among chemica! engineers)#
'eng%:obinson EOS ("ery $o$u!ar among $etro!eum and natura! gas engineers)
Hee$ in mind that# once you ha"e an EOS# you can deri"e "irtua!!y any $ro$erty of the f!uid
Redlich!"#on$ ES %&'(')
"d6 cubic equation of state had to *ait a!most <00 years before a rea!# successfu! im$ro"ement *as
introduced to it As *e stated before# this $rogress occurred once researchers committed themse!"es to
finding the em$irica! tem$erature de$endency of the attraction $arameter @aA $ro$osed by "an der 6aa!s (n
contrast# "ery !itt!e attention has been $aid to modifying the $arameter @bA for co%"o!ume (t ma-es a !ot of
sense that @bA *ou!d not be modified by tem$erature# because it re$resents the volume of the mo!ecu!es#
*hich shou!d not be affected by their -inetic energy (measured in terms of tem$erature)
The "ery first note*orthy successfu! modification to the attraction $arameter came *ith the $ub!ication of the
equation of state of :ed!ich%H*ong in <IJI :ed!ich and H*ong re"ised "an der 6aa!s EOS and $ro$osed
the fo!!o*ing e)$ression=
#10.1&
+otice that the fundamenta! change they introduced *as to the functiona! form of N'attraction (equation K8#
Modu!e K) Additiona!!y# they introduced the co%"o!ume @bA into the denominator of this functiona! form
The im$ortant conce$t here is that the attraction $arameter @aA of "an der 6aa!s needed to be made a
function of tem$erature before any cubic EOS *as ab!e to do a better 9ob of quantitati"e!y matching
e)$erimenta! data This *as a rea!i&ation that "d6 himse!f had suggested# but no actua! functiona!
de$endency had been introduced unti! the :ed!ich%H*ong EOS
6e -no* *hat fo!!o*s at this $oint To come u$ *ith an e)$ression for @aA and @bA of equation (<0<)# *e
a$$!y the critica!ity conditions to this EOS As *e reca!!# im$osing the critica!ity conditions a!!o*s us to re!ate
the coefficients @aA and @bA to the critica! $ro$erties ('c# Tc) of the substance Once *e ha"e done that# *e
obtain the definition of @aA and @bA for the :ed!ich%H*ong EOS#
#10.)a&
#10.)b&
This EOS radica!!y im$ro"ed# in a quantitati"e sense# the $redictions of "d6 EOS 6e no* reca!! that "d6%
ty$e equations are cubic because they are cubic $o!ynomia!s in mo!ar "o!ume and com$ressibi!ity factor (t
comes as no sur$rise then# that *e can transform equation (<0<) into=
#10.,&
and# by defining the fo!!o*ing $arameters#
#10.,a&
##10.,b&
and introducing the com$ressibi!ity factor definition ( )# *e get=
#10.-&
6e may a!so "erify the t*o%$arameter corres$onding state theory by introducing equations (<0D) and (<02)
into (<0J)#
#10..&
(n equation (<0O) *e can obser"e the same thing that *e sa* *ith "d6 EOS= gases at corres$onding
states ha"e the same $ro$erties Equation (<0O) is $articu!ar!y c!ear about it= any t*o different gases at the
same 'r# Tr condition ha"e the same com$ressibi!ity factor
Lust as any other cubic equation of state# equations (<0<) through (<0O)# as they stand# are to be a$$!ied to
$ure substances 1or mi)tures# ho*e"er# *e a$$!y the same equation, but *e im$ose certain mi)ing ru!es to
obtain @aA and @bA# *hich are functions of the $ro$erties of the $ure com$onents Strict!y s$ea-ing# *e create
a ne* @$seudoA $ure substance that has the a"erage $ro$erties of the mi)ture :ed!ich%H*ong $reser"ed
the same mi)ing ru!es that "d6 $ro$osed for his EOS=
, #10./a&
#10./b&
+atura!!y# :ed!ich and H*ong did not ha"e the !ast *ord on $ossib!e im$ro"ements to the "d6 EOS The
:ed!ich%H*ong EOS# as sho*n here# is no !onger used in $ractica! a$$!ications :esearch continued and
brought *ith it ne* attem$ts to im$ro"e the :H EOS After more than t*o decades# a modified :H EOS *ith
"ery good $otentia! *as de"e!o$ed The Soa"e%:H EOS *as born
Soave!Redlich!"#on$ ES %&'*+)
(n <IK2# Soa"e $ro$osed an im$ortant modification to the :H EOS . or sha!! *e say# a modification to "d6
EOS 8et*een the time of "d6 EOS and :ed!ich%H*ong/s# a ne* conce$t for f!uid characteri&ation *as
being discussed 'it&er had introduced the conce$t of acentric factor in <IOO
A!! modifications to the "d6 EOS had focused on the tem$erature de$endency of the attracti"e $arameter
Soa"e e)$anded this by $ro$osing a t*o%"ariab!e de$endency for @aA=
#10.0&
(t *as the first time that @aA *as e)$ressed not on!y as a function of tem$erature# but a!so as a function of
the sha$e (s$hericity) of the mo!ecu!es (through *# 'it&er/s acentric factor) As *e reca!!# 'it&er/s acentric
factor is a measure of the configuration and s$hericity of the mo!ecu!e (t can a!so be seen as a measure of
the deformity of the mo!ecu!e
The Soa"e%:ed!ich%H*ong EOS is gi"en by the e)$ression=
#10.1a&
5i-e a!! cubic equations of state# the S:H EOS is a!so e)$!icit in $ressure +otice# for e)am$!e# ho* the S:H
EOS readi!y becomes=
#10.1b&
*here#
#10.1c&
The inf!uence of acentric factor and tem$erature on the attracti"e term is introduced no* through @aA 6hat
do *e do ne)t7 6e a$$!y the critica!ity conditions to equation (<08b) +otice that e)$ression (<08c)
becomes unity at TrB<# throughout the critica! isotherm 6e obtain=
#10.2a&
#10.2b&
+o* *e sho* the cubic form (in com$ressibi!ity factor) of Soa"e%:ed!ich%H*ong EOS Mefining#
#10.10a&
# #10.10b&
*e are ab!e to obtain=
#10.11&
1or mi)tures# Soa"e $ro$osed a @!itt!eA modification to the mi)ing ru!es *ith *hich *e ha"e dea!t *ith so far
by introducing the use of @binary interaction $arametersA (-i9)=
, #10.1)a&
#10.1)b&
The use of binary interaction $arameters (-i9) generated a !ot of resistance u$on their first introduction This
is because there is no ana!ytica!# science%based deri"ation that 9ustifies their e)istence +o*adays# they are
regarded 9ust as they are# em$irica! factors used to tune equations of state and ma-e them match
e)$erimenta! data for mi)tures This has become the heuristic 9ustification for their e)istence= *ith them#
EOS can do a better 9ob of matching e)$erimenta! data Heuristically s$ea-ing# they are a measure of
interaction bet*een a $air of dis!i-e mo!ecu!es 8ased on this @definition#A their "a!ue is &ero for $airs of
mo!ecu!es that are a!i-e Actua!!y# this is no more than a mathematica! requirement in order for equation
(<0<2a) to gi"e *hen 9Bi The determination of -i9 is based on e)$erimenta! data from
binary systems, @-i9A resu!ts from the "a!ue that a!!o*s the gi"en equation of state (through the e)$ression in
<0<2a) to yie!d the c!osest match These "a!ues are assumed to be constant (and so are used) *hen the
same t*o com$onents are $art of a more com$!e) mu!ti%com$onent mi)ture
Action Item
Ans*er the fo!!o*ing $rob!ems# and submit your ans*ers to the dro$ bo) in A+4E5 that has been created
for this modu!e
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Problem Set
< An engineer is see-ing your ad"ice on *hich EOS he shou!d use to mode! "arious hydrocarbon
mi)tures he is dea!ing *ith 0e has access to a $rogram that $ro"ides him *ith se"era! o$tions for
different cubic EOS 0e $resents you *ith the fo!!o*ing !ist=
o A s*eet natura! gas from +igeria
o A sour natura! gas (high 3O2# 02S contents)
o 1!ue gas
6hich EOS *ou!d you recommend him to use for each of these cases7
Module Cubic EOS and Their Behavior (III)
Module Goals
Module Objective: To assess the re!ati"e merit of a$$!ying the most common EOS
Pen$!Robinson ES %&'*,)
The 'eng%:obinson EOS has become the most $o$u!ar equation of state for natura! gas systems in the
$etro!eum industry Muring the decade of the <IK0/s# M 'eng *as a 'hM student of 'rof M8 :obinson at
the Qni"ersity of 3a!gary (3anada) The 3anadian Energy 8oard s$onsored them to de"e!o$ an EOS
s$ecifica!!y focused on natura! gas systems 6hen you com$are the $erformance of the ': EOS and the
S:H EOS# they are $retty c!ose to a tie, they are @nec- to nec-#A e)ce$t for a s!ight!y better beha"ior by the
': EOS at the critica! $oint A s!ight!y better $erformance around critica! conditions ma-es the ': EOS
some*hat better suited to gas>condensate systems
'eng and :obinson introduced the fo!!o*ing modified "d6 EOS=
#11.1a&
or# e)$!icit!y in $ressure#
#11.1b&
*here=
#11.1c&
'eng and :obinson conser"ed the tem$erature de$endency of the attracti"e term and the acentric factor
introduced by Soa"e 0o*e"er# they $resented different fitting $arameters to describe this de$endency
(equation J<<c)# and further mani$u!ated the denominator of the $ressure correction (attracti"e) term As *e
ha"e seen before# coefficients @aA and @bA are made functions of the critica! $ro$erties by im$osing the
critica!ity conditions This yie!ds=
#11.)a&
#11.)b&
The ': cubic e)$ression in G becomes=
#11.,a&
*here=
#11.,b&
#11.,c&
Simi!ar to S:H# the ': mi)ing ru!es are=
, #11.-a&
#11.-b&
*here binary interaction $arameters (-i9) again $!ay the im$ortant em$irica! ro!e of he!$ing to better fit
e)$erimenta! data Mue to the em$irica! character of these interaction $arameters# -i9/s ca!cu!ated for ':
EOS are un!i-e!y to be the same as the -i9/s ca!cu!ated for S:H EOS for the same $air of mo!ecu!es
Comparative Assessment o- R". SR". and PR ES
O"er the years# these EOS ha"e been tested# and some com$arisons can be made As an engineer# you
ha"e to be ab!e to decide *hich EOS best fits your $ur$oses
Redlic! 34ong EO:
4enera!!y good for gas $hase $ro$erties
'oor for !iquid $hase $ro$erties
8etter *hen used in con9unction *ith a corre!ation for !iquid $hase beha"ior
Satisfactory for gas $hase fugacity ca!cu!ation R 'r E Tr>D
Satisfactory for entha!$y de$arture and entro$y de$arture ca!cu!ations
oave Redlic! 34ong 5 +eng Robinson EO
Ser"e simi!ar functions as the :ed!ich H*ong EOS but require more $arameters
': obtains better !iquid densities than S:H
O"era!!# ': does a better 9ob (s!ight!y) for gas and condensate systems than S:H 0o*e"er# for
$o!ar systems# S:H a!*ays ma-es a better $rediction# but in the $etro!eum engineering business
*e do not usua!!y dea! *ith those
/0
c
1 as a Measure o- Goodness o- an ES
Some "a!ues for critica! com$ressibi!ity factors are sho*n be!o*=
Experimental Zc or !arious Substances
3O2 B 02KJJ
30J B 02862
3206 B 02KID
n3O B 026ID
n36 B 026OI
The "a!ues of critica! com$ressibi!ity factors sho*n here are re!ati"e!y c!ose to each other# but# in actua!ity#
they are different They are# in fact# substance%de$endent This is a stri-ing finding if *e reca!! our high!y%
$raised 'rinci$!e of 3orres$onding States Midn/t *e say that at the same reduced conditions# a!! substances
@mustA ha"e# at the "ery !east# the same com$ressibi!ity factor# G7 0ere is a case *here *e ha"e different
substances at the same corres$onding states ('r B Tr B <# right at the critica! $oint) but different @GA "a!ues
Aftera!! the 3orres$onding States 'rinci$!e is not infa!!ib!e (as *as stated by 'it&er) As *e reca!!# he
$ro$osed the introduction of a third $arameter (acentric factor) into the corres$onding state definition to
a!!e"iate these -inds of @$rob!emsA
At the "ery !east# *e may say that the "a!ues of Gc (com$ressibi!ity factor at the critica! $oint) of different
substances are @c!ose enoughA among themse!"es That is# they are not @gross!y different#A so as to say that
the a$$!ication of the t*o%$arameter corres$onding states $rinci$!e *ou!d be outrageous at the critica! $oint
The fact of the matter is# as a consequence of the 3orres$onding States 'rinci$!e# a!! cubic EOS $redict a
@uniqueA and @uni"ersa!A "a!ue of G at the critica! $oint# regard!ess of the substance The !ist be!o* te!!s us
ho* they $erform
"#niversal$ Zc predicted b% dierent EOS
(dea! EOS B <000
"d6 EOS B 0DKO
:H EOS B 0DDD
S:H EOS B 0DDD
': EOS B 0D0<
1rom the !ist abo"e# *e *ou!d ha"e been e)$ecting some -ind of @a"erageA Gc of 02K or so 8ut none of the
equations of state *e ha"e studied is ca$ab!e of $redicting a "a!ue that !o* The @bestA 9ob is done by ':
EOS# *hich $ro"ides the @c!osestA match to the rea! "a!ues obser"ed for most substances This i!!ustrates
*hy the ': EOS $erforms some*hat better near critica! conditions
Advanta$es o- 2sin$ Cubic E3uations o- State
A!! cubic equations of state ha"e their foundation in "d6 EOS The use of cubic equations of state has
become *ides$read because of their ad"antages=
Sim$!icity of a$$!ication
On!y a fe* $arameters need to be determined
5o* com$utationa! o"erhead is required to im$!ement them This *as a critica! issue# $articu!ar!y in
the ear!y stages of com$uters, it is not rea!!y anymore +e"erthe!ess# this feature is sti!! a @$!usA
The engineer using cubic equations of state must a!so be a*are of the disad"antages that they a!! share
The most im$ortant ones are the !imited accuracy that they can $ro"ide# $articu!ar!y for com$!e) systems (n
these cases# the $rocurement of em$irica! ad9ustments through the use of the binary interaction $arameters
(-i9) is essentia!
Solution 4echni3ues -or Cubic E5pressions and Root 6indin$
0o$efu!!y# *e ha"e con"inced you that the use of cubic equations of state can re$resent a "ery meaningfu!
and ad"antageous *ay of mode!ing the '2T beha"ior of $etro!eum f!uids 6hat *e need no* are the too!s
that *i!! a!!o* us to get the information that *e *ant out of them E"en though cubic equations of state are
e)$!icit in $ressure# $ressure is not the common un-no*n to be ca!cu!ated in the ty$ica! $rob!em (n the most
common $rob!em# $ressure and tem$erature are -no*n and *e *ant either mo!ar "o!ume (or its reci$roca!#
mo!ar density) or com$ressibi!ity factor (the most !i-e!y case) Therefore# *e are faced "ery often *ith the
need to so!"e for the roots of a cubic e)$ression 0ere *e $resent a number of a$$roaches that may be
fo!!o*ed
6nal*tical sc!e"e
4i"en the cubic $o!ynomia! *ith rea! coefficients= )
D
C a)
2
C b) C c B 0# the first ste$ is to ca!cu!ate the
$arameters=
and #11..&
+o* !et M B :
2
S T
D
be the discriminant. 6e then consider the fo!!o*ing cases=
a (f M E 0 (:
2
E T
D
)# the $o!ynomia! has three rea! roots 1or this case# com$ute
and ca!cu!ate the three distinct rea! roots as=
#11./a&
#11./b&
#11./c&
+ote that )<# )2# )D are not gi"en in any s$ecia! order# and that has to be ca!cu!ated in radians
b (f M F 0 (:
2
F T
D
)# the $o!ynomia! has on!y one rea! root 3om$ute=
#11.0a&
#11.0b&
and ca!cu!ate the rea! root as fo!!o*s=
#11.0c&
T*o com$!e) roots (com$!e) con9ugates) may be found as *e!! 0o*e"er# they are of no interest for our
$ur$oses# and thus no formu!as are $ro"ided Such formu!as can be found in the fo!!o*ing suggested
readings=
60 'ress# SA Teu-o!s-y# 6T 2etter!ing# 8' 1!annery# Numerical Recipes in Fortran, 2
nd

Edition# 3ambridge Qni" 'ress# (<II2)# $ <KI
S$iege!# M# 5iu# L# athematical handboo! of formulas and tables# 2
nd
Edition# Schaum/s Out!ine
Series# Mc4ra* 0i!!# $<0
Sometimes# the equations for S and T !isted abo"e cause $rob!ems *hi!e $rogramming This usua!!y
ha$$ens *hene"er the com$uter>ca!cu!ator $erforms the cubic root of a negati"e quantity (f you *ant to
a"oid such a situation# you may com$ute S/ and T/ instead=
(ma-ing T/B0 *hen S/B0)
*here=
abs(:) B Abso!ute "a!ue of :
and
sign(:) B (C<) or (S <) if : is $ositi"e or negati"e res$ecti"e!y
(t may be defined as=
sign(:) B :>Abs(:)
and then the rea! root is=
Hee$ in mind the fo!!o*ing usefu! re!ationshi$s among the roots of any cubic e)$ression=
)< C )2 C )D B S a#11.1a&
)<)2 C )2)D C )D)< B Cb#11.1b&
)< )2 )D B S c#11.1c&
Sel&Chec'
Test your understanding of cubic root ca!cu!ations by ana!ytica! means by so!"ing the fo!!o*ing e)am$!es
6ith genera! cubic e)$ressions#
)
D
S 6)
2
C <<) S 6 B 0 BF
)< B <
)2 B 2
)D B D
)
D
C K)
2
C JI) C DJD B 0
)< B S K
)2 B 0 C K i
)D B 0 S K i
)
D
C 2)
2
C D) C J B 0 BF
)< B S < 6O06D
)2 B S 0<KJ68O C <OJ68K i
)D B S 0<KJ68O S <OJ68K i
*ith EOS in terms of "o!ume (")# for a $ure com$onent#
"
D
S K86ID "
2
C <DDKK< " S 6ODOJ B 0
BF One rea! root (one $hase)#
"< B OKDOK "D S <O6D68 "2 C D0D<O" S <J8<0J B 0
BF T*o $ossib!e $hases (three rea! roots)#
"< B 080KO82 (!iquid $hase)
v" # $.%&$'( )re*ected+
"D B <DJ6KO(gas $hase)
*ith EOS in terms of the com$ressibi!ity factor (&)# for a $ure com$onent#
&
D
S <0OIO &
2
C 022<O & S 00<D<K B 0
BF One $hase#
& B 080JO
&
D
S &
2
C 008I & S 000<D B 0
BF T*o $ossib!e $hases#
&!iquid B 00<8D0<2
&) B 00K8660I (use!ess)
&"a$or B 0I0D0D8
7u"erical c!e"e
The +e*ton%:a$hson method $ro"ides a usefu! scheme for so!"ing for a non%e)$!icit "ariab!e from any form
of equation (not on!y cubic ones) +e*ton%:a$hson is an iterati"e $rocedure *ith a fast con"ergence#
a!though it is not a!*ays ca$ab!e of $ro"iding an ans*er . because a first guess c!ose enough to the actua!
ans*er must be $ro"ided
(n so!"ing for @)A in any equation of the ty$e f())B0# the method $ro"ides a ne* estimate (ne* guess) c!oser
to the actua! ans*er# based on the $re"ious estimate (o!d guess) This is *ritten as fo!!o*s=
#11.2&
3onsidering a cubic equation f()) B )
D
C a)
2
C b) C c B 0# the $re"ious equation ta-es the form=
#11.10&
The iterations continue unti! no significant im$ro"ement for @)ne*A is achie"ed# ie# U )ne* S )o!d U E to!erance
An educated guess must be $ro"ided as the starting "a!ue for the iterations (f you are so!"ing a cubic
equation in G (com$ressibi!ity factor)# it is usua!!y recommend to ta-e G B b'>:T as the starting guess for the
com$ressibi!ity of the !iquid $hase and G B < for the "a$or root
e"i8anal*tical c!e"e
(f you used the $re"ious numerica! a$$roach to ca!cu!ate one of the roots of the cubic e)$ression# the semi%
ana!ytica! scheme can gi"e you the other t*o rea! roots (*hen they e)ist) 8y using the re!ationshi$s gi"en
before# *ith the "a!ue V)</ as the root a!ready -no*n# the other t*o roots are ca!cu!ated by so!"ing the system
of equations=
)2 C )D B S a S )<#11.11a&
)2)D B S c>)< #11.11b&
*hich !eads to a quadratic e)$ression
This $rocedure can be reduced to the fo!!o*ing ste$s=
< 5et )
D
C a)
2
C b) C c B 0 be the origina! cubic $o!ynomia! and @EA the root *hich is a!ready -no*n ()<
B E) Then# *e may factori&e such a cubic e)$ression as=
() S E) ()
2
C 1) C 4) B 0#11.1)a&
*here=
1 B a C E#11.1)b&
4 B S c > E#11.1)c&
2 So!"e for )2# )D by using the quadratic e)$ression formu!ae#
)< B E #11.1,a&
#11.1,b&
#11.1,b&
Action Item
for this modu!e
Please note:
date
Problem Set
< 6hat is the meaning of Gc7 (critica! com$ressibi!ity factor) 6hy do you thin- it is used as a
measure of the $erformance of an EOS7
2 6hat do you thin- shou!d be the "a!ue of @GA at the critica! $oint7 (s it @oneA (<)7 6hy7 (s this to be
e)$ected7
Module Properties o (atural )as and Condensates
(I)
Module Goals
Module Goal: To high!ight the im$ortant $ro$erties used to characteri&e natura! gas and condensate
systems
Module Objective: To $resent the most $o$u!ar mode!s for estimating $ro$erties of natura! gas and
condensate systems
(I)
Introduction
1!uid $ro$erties are used to characteri&e the condition of a f!uid at a gi"en state A re!iab!e estimation and
descri$tion of the $ro$erties of hydrocarbon mi)tures is fundamenta! in $etro!eum and natura! engineering
ana!ysis and design 1!uid $ro$erties are not inde$endent# 9ust as $ressure# tem$erature# and "o!ume are
not inde$endent of each other Equations of State $ro"ide the means for the estimation of the '%2%T
re!ationshi$# and from them many other thermodynamic $ro$erties can be deri"ed 3om$ositions are usua!!y
required for the ca!cu!ation of the $ro$erties of each $hase 1or a 25E system# using the too!s *e ha"e
discussed in the $re"ious !ectures# *e are ready to $redict some im$ortant $ro$erties of both the !iquid
(condensate) and "a$or (natura! gas) $hases . by means of the -no*n "a!ues of com$osition of both
$hases Some of the most re!e"ant are discussed ne)t
(I)
Molecular Wei$ht
The mo!ecu!ar *eight (M6) of each of the $hases in a 25E system is ca!cu!ated as a function of the
mo!ecu!ar *eight of the indi"idua! com$onents (M6i)# $ro"ided that both the com$osition of the gas (yi) and
the !iquid ()i) are -no*n=
#11.1a&
#11.1b&
(I)
7ensity
Mensity is customari!y defined as the amount of mass contained in a unit "o!ume of f!uid Mensity is the
sing!e%most im$ortant $ro$erty of a f!uid# once *e rea!i&e that most other $ro$erties can be obtained or
re!ated to density 8oth s$ecific "o!ume and density . *hich are in"erse!y $ro$ortiona!!y re!ated to each
other . te!! us the story of ho* far a$art the mo!ecu!es in a f!uid are from each other 1or !iquids# density is
high . *hich trans!ates to a "ery high mo!ecu!ar concentration and short intermo!ecu!ar distances 1or
gases# density is !o* . *hich trans!ates to !o* mo!ecu!ar concentrations !arge intermo!ecu!ar distances
The question then is= 4i"en this# ho* can *e obtain this a!!%im$ortant $ro$erty ca!!ed density7 This ta-es us
bac- to Equations of State (EOS) Since "ery ear!y times# there ha"e been corre!ations for the estimation of
density of the !iquids (oi!# condensates) and gases>"a$ors (dry gases# *et gases) (n modern times#
equations of state (EOS) are a natura! *ay of obtaining densities The density of the f!uid Vf/ is ca!cu!ated
using its com$ressibi!ity factor (Gf) as $redicted by an a$$ro$riate equation of state 1rom the rea! gas !a*#
the density can be e)$ressed as=
#11.)&
*here= M6f is the mo!ecu!ar *eight of f!uid Vf/ E)$ression (<82) is used for both the gas and !iquid density
(n either case# the $ro$er "a!ue for M6f (either M6g or M6!) and Gf (either Gg or Go) has to be used This
ta-es us bac- to the discussion of equations of state 1rom Equation (<82) it is c!ear that a!! that *e need is
the G%factor
The a!!%im$ortant $arameter to ca!cu!ate density is the G%factor# both for the !iquid and "a$or $hases The
re!ation bet*een !iquid beha"ior and G%factor is not ob"ious# because G%factor has been traditiona!!y defined
for gases 0o*e"er# *e can get @GA for !iquids @GA is# indeed# a measure of de$arture from the idea! gas
beha"ior 1air enough# for defining @GA for !iquids# *e sti!! measure the de$arture of !iquid beha"ior from idea!
gas beha"ior A @!iquid stateA is a tremendous de$arture from idea!%gas conditions# and as such# @GA for a
!iquid is a!*ays "ery far from unity Ty$ica! "a!ues of @GA for !iquids are sma!!
Equations of State ha"e $ro"en "ery re!iab!e for the estimation of "a$or densities# but they do not do as
good a 9ob for !iquid densities There is actua!!y a debate among different authors about the re!iabi!ity of G%
factor estimations for !iquids using EOS (n fact# $eo$!e sti!! be!ie"e the EOS are not re!iab!e for !iquid density
$redictions and that *e shou!d use corre!ations instead 0o*e"er# 'eng%:obinson EOS $ro"ides fair
estimates for "a$or and !iquid densities as !ong as *e are dea!ing *ith natura! gas and condensate systems
Em$irica! corre!ations for G%factor for natura! gases *ere de"e!o$ed before the ad"ent of digita! com$uters
A!though their use is in dec!ine# they can sti!! be used for fast estimates of the G%factor The most $o$u!ar of
such corre!ations inc!ude those of 0a!!%;arborough and Mranchu-%Abou%Hassem
3hart !oo-%u$ is another means of determining G%factor of natura! gas mi)tures These methods are
in"ariab!y based on some ty$e of corres$onding states de"e!o$ment According to the theory of
corres$onding states# substances at corres$onding states *i!! e)hibit the same beha"ior (and hence the
same G%factor) The chart of Standing and Hat& is the most common!y used G%factor chart for natura! gas
mi)tures
Methods of direct ca!cu!ation using corres$onding states ha"e a!so been de"e!o$ed# ranging from
corre!ations of chart "a!ues to so$histicated equation sets based on theoretica! de"e!o$ments
0o*e"er# the use of equations of state to determine G%factors has gro*n in $o$u!arity as com$uting
ca$abi!ities ha"e im$ro"ed Equations of state re$resent the most com$!e) method of ca!cu!ating G%factor#
but a!so the most accurate A "ariety of equations of state ha"e been de"e!o$ed to describe gas mi)tures#
ranging from the idea! EOS (*hich yie!ds on!y one root for the "a$or and $oor $redictions at high $ressures
and !o* tem$eratures)# cubic EOS (*hich yie!ds u$ to three roots# inc!uding one for the !iquid $hase)# and
more ad"anced EOS such as 86: and A4A8
Re9erences:
0a!! H# and ;arborough# 5 (<IKD)# @A +e* Equation of State for G%factor 3a!cu!ationsA# Oi! and 4as Lourna!#
Lune <IKD# $$ 82%I2
Mranchu-# ' and Abou%Hassem# L (<IKO)# @3a!cu!ation of G%factors for +atura! 4ases Qsing Equations%of%
StateA# L3'T# Lu!y%Se$tember <IKO# $ DJ%D6
Standing# M and Hat&# M (<IJ2)# @Mensity of +atura! 4asesA# Trans A(ME# " <J6# $$ <J0%<JI
(I)
Speci-ic Gravity
S$ecific gra"ity is defined as the ratio of f!uid density to the density of a reference substance# both defined at
the same $ressure and tem$erature These densities are usua!!y defined at standard conditions (<JK $sia
and 60W1) 1or a condensate# oi! or a !iquid# the reference substance is water=
#11.,&
The "a!ue of *ater density at standard conditions is 62J !bm>ft
D
a$$ro)imate!y 1or a natural gas# or any
other gas for this matter# the reference substance is air=
#11.,a&
Or# equi"a!ent!y# substituting Equation (<82) e"a!uated at standard conditions ( for most gases)#
#11.,b&
*here the "a!ue of the mo!ecu!ar *eight for air is M6air B 28I6 !bm>!bmo! S$ecific gra"ity is nondimensiona!
because both numerator and denominator ha"e the same units
(I)
API
'etro!eum and +atura! 4as Engineers a!so use another gra"ity term *hich is ca!!ed A'( gra"ity (t is used for
!iquids (eg# condensates) and is defined as=
#11.-&
8y definition (see Equation <8D)# the s$ecific gra"ity of *ater is unity Therefore# *ater has an A'( gra"ity of
<0 The A'( gra"ity of <0 is associated *ith "ery hea"y# a!most as$ha!tic# oi!s 5ight crude oi!s ha"e an A'(
greater than or equa! to JOW ,ondensate gra"ities range bet*een O0W and K0W A'( 5iquid condensates are
norma!!y !ight in co!or
(I)
8olumetric 6actors %B
o
and B
$
)
Mue to the dramatica!!y different conditions $re"ai!ing at the reser"oir *hen com$ared to the conditions at
the surface# *e do not e)$ect that < barre! of f!uid at reser"oir conditions cou!d contain the same amount of
matter as < barre! of f!uid at surface conditions 2o!umetric factors *ere introduced in $etro!eum and natura!
gas ca!cu!ations in order to readi!y re!ate the volume of f!uids that are obtained at the surface (stoc- tan-) to
the "o!ume that the f!uid actua!!y occu$ied *hen it *as com$ressed in the reser"oir
1or e)am$!e# the "o!ume that a live oil occu$ies at the reser"oir is more than the "o!ume of oi! that !ea"es
the stoc- tan- at the surface This may be counter%intuiti"e 0o*e"er# this is a resu!t of the e"o!ution of gas
from oi! as $ressure decreases from reser"oir $ressure to surface $ressure (f an oi! had no gas in so!ution
(ie# a dead oil)# the "o!ume that it *ou!d occu$y at reser"oir conditions is !ess than the "o!ume that it
occu$ies at the surface (n this case# on!y !iquid com$ressibi!ity $!ays a ro!e in the change of "o!ume
$!e 9or"ation volu"e 9actor o9 a natural gas (8g) re!ates the "o!ume of < !bmo! of gas at reser"oir
conditions to the "o!ume of the same !bmo! of gas at standard conditions# as fo!!o*s=
#11..&
Those "o!umes are# e"ident!y# the s$ecific mo!ar "o!umes of the gas at the gi"en conditions The reci$roca!
of the s$ecific mo!ar "o!ume is the mo!ar density# and thus# Equation (<8O) cou!d be *ritten=
#11./&
(ntroducing the definition for densities in terms of com$ressibi!ity factor#
#11.0&
Therefore# reca!!ing that #
X:31>S31Y#11.1&
4as formation "o!ume factors can be a!so e)$ressed in terms of X:8>S31Y (n such a case# < :8 B O6<O
:31 and *e *rite=
X:31>S31Y#11.2&
The formation "o!ume factor of an oil or condensate (8o) re!ates the "o!ume of < !bmo! of !iquid at reser"oir
conditions to the "o!ume of that !iquid once it has gone through the surface se$aration faci!ity
#11.10&
The tota! "o!ume occu$ied by < !bmo! of !iquid at reser"oir conditions (2o)res can be ca!cu!ated through the
com$ressibi!ity factor of that !iquid# as fo!!o*s=
*here n B < !bmo!##11.11&
Q$on se$aration# some gas is going to be ta-en out of the !iquid stream feeding the surface faci!ity 5et us
ca!! @nstA the mo!es of !iquid !ea"ing the stoc- tan- $er mo!e of feed entering the se$aration faci!ity The
"o!ume that < !bmo! of reser"oir !iquid is going to occu$y after going through the se$aration faci!ity is gi"en
by=
#11.1)&
0ere *e assume that the !ast stage of se$aration# the stoc- tan-# o$erates at standard conditions
(ntroducing Equations (<8<2) and (<8<<) into (<8<0)# *e end u$ *ith=
#11.1,&
or#
X:8>ST8Y#11.1-&
'!ease notice that (Go)sc . un!i-e Gsc for a gas . is ne"er equa! to one Oi! formation "o!ume factor can be
a!so seen as the "o!ume of reser"oir f!uid required to $roduce one barre! of oi! in the stoc- tan-
(I)
Isothermal Compressibilities
The isotherma! com$ressibi!ity of a f!uid is defined as fo!!o*s=
##11.1.&
This e)$ression can be a!so gi"en in term of f!uid density# as fo!!o*s=
#11.1/&
For li:uids; the "a!ue of isotherma! com$ressibi!ity is "ery sma!! because a unitary change in $ressure
causes a "ery sma!! change in "o!ume for a !iquid (n fact# for s!ight!y com$ressib!e !iquid# the "a!ue of
com$ressibi!ity (co) is usua!!y assumed inde$endent of $ressure Therefore# for sma!! ranges of $ressure
across *hich co is near!y constant# Equation (<8<6) can be integrated to get=
#11.10&
(n such a case# the fo!!o*ing e)$ression can be deri"ed to re!ate t*o different !iquid densities ( # ob) at
t*o different $ressures ($# $b)=
#11.11&
The 2asque&%8eggs corre!ation is the most common!y used re!ationshi$ for co
For natural gases; isotherma! com$ressibi!ity "aries significant!y *ith $ressure 8y introducing the rea! gas
!a* into Equation (<8<6)# it is easy to $ro"e that# for gases=
#11.12&
+ote that for an idea! gas# cg is 9ust the reci$roca! of the $ressure @cgA can be readi!y ca!cu!ated by gra$hica!
means (chart of G "ersus ') or by introducing an equation of state into Equation (<8<I)
(I)
Sur-ace 4ension
Surface tension is a measure of the surface free energy of !iquids# ie# the e)tent of energy stored at the
surface of !iquids A!though it is a!so -no*n as interfacia! force or interfacia! tension# the name surface
tension is usua!!y used in systems *here the !iquid is in contact *ith gas
Tua!itati"e!y# it is described as the force acting on the surface of a !iquid that tends to minimi&e the area of
its surface# resu!ting in !iquids forming dro$!ets *ith s$herica! sha$e# for instance Tuantitati"e!y# since its
dimension is of force o"er !ength (!bf>ft in Eng!ish units)# it is e)$ressed as the force (in !bf) required to brea-
a fi!m of < ft of !ength Equi"a!ent!y# it may be restated as being the amount of surface energy (in !bf%ft) $er
square feet
Hat& et al. (<IOI) $resented the Mac!eod%Sudgen equation for surface tension ( ) ca!cu!ations in dynes>cm
for hydrocarbon mi)tures=
#11.)0&
*here=
'chi B 'arachor of com$onent @iA#
)i B mo!e fraction of com$onent @iA in the !iquid $hase#
yi B mo!e fraction of com$onent @iA in the gas $hase
(n order to e)$ress surface tension in fie!d units (!bf>ft)# mu!ti$!y the surface tension in (dynes>cm) by
68O2<KK)<0
%D
The $arachor is a tem$erature inde$endent $arameter that is ca!cu!ated e)$erimenta!!y
'arachors for $ure substances ha"e been $resented by 6einaug and Hat& (<IJD) and are !isted in Tab!e
<8<
$able 11.1. +arac!ors 9or pure substances #<einaug and 3at=; 12-,&
Co"ponent +arac!or
3O2 K80
+2 J<0
3< KK0
32 <080
3D <O0D
i3J <8<O
n3J <8II
i3O 22O0
n3O 2D<O
n36 2K<0
n3K D<2O
n38 DO<O
6einaug and Hat& (<IJD) a!so $resented the fo!!o*ing em$irica! re!ationshi$ for the $arachor of
hydrocarbons in terms of their mo!ecu!ar *eight=
#11.)1&
This corre!ation may be used for $seudo%com$onents or for those hydrocarbons not sho*n in Tab!e
<8<
(I)
Action Item
Ans*er the fo!!o*ing $rob!em# and submit your ans*er to the dro$ bo) in A+4E5 that has been created for
this modu!e
Please note:
;our ans*er must be submitted in the form of a Microsoft 6ord document
date
Problem Set
< 6hich of a!! the $ro$erties *e ha"e studied so far *ou!d you use to com$are and distinguish
among *et natura! gas# dry natura! gas# and gas%condensate systems7 E)$!ain *hy
(II)
Module Goals
Module Goal: To high!ight the im$ortant $ro$erties used to characteri&e natura! gas and condensate
systems
Module Objective: To $resent the most $o$u!ar mode!s for estimating $ro$erties of natura! gas and
condensate systems
(II)
9eat Capacities
The constant volume heat ca$acity is defined by=
#12.1&
To see the $hysica! significance of the constant "o!ume heat ca$acity# !et us consider a < !bmo! of gas *ithin
a rigid%*a!! (constant "o!ume) container 0eat is added to the system through the *a!!s of the container and
the gas tem$erature rises (t is e"ident that the tem$erature rise ( ) is $ro$ortiona! to the amount of heat
added#
#12.)&
(ntroducing a constant of $ro$ortiona!ity @c"A#
#12.,&
(n our e)$eriment# no *or- *as done because the boundaries (*a!!s) of the system remained unchanged
A$$!ying the first !a* of thermodynamics to this c!osed system# *e ha"e=
#12.-&
Therefore# for infinitesima! changes#
#12..&
As *e ha"e seen# constant "o!ume heat ca$acity is the amount of heat required to raise the tem$erature of
a gas by one degree while retaining its volume
5et us no* consider the same < !bmo! of gas confined in a $iston%cy!inder equi$ment (ie# a system *ith
non%rigid *a!!s or boundaries) 6hen heat is added to the system# the gas tem$erature rises and the gas
e)$ands so that the pressure in the system remains the same at any time The $iston dis$!aces a "o!ume
2 and the gas increases its tem$erature in degrees Again# the tem$erature rise ( T) is $ro$ortiona! to
the amount of heat added# and the ne* constant of $ro$ortiona!ity *e use here is @c$A#
#12./&
This time# some *or- *as done because the boundaries (*a!!s) of the system changed from their origina!
$osition A$$!ying the first !a* of thermodynamics to this c!osed system# *e ha"e that=
#12.0&
(f the $ressure remained the same both inside and outside the container# the system made some *or-
against the surroundings in the amount of 6B' 2 (ntroducing (<IK) into (<I6)#
#12.1&
The !eft hand side of this equation re$resents the definition of enthalpy change ( 0) for a constant%$ressure
$rocess Therefore=
#12.2&
1ina!!y# for infinitesima! changes#
#12.10&
The function @c$A is ca!!ed the constant pressure heat capacity The constant $ressure heat ca$acity is the
amount of heat required to raise the tem$erature of a gas by one degree while retaining its pressure
The units of both heat ca$acities are (8tu>!bmo!%W1) and (ca!>gr%W3) Their "a!ues are never equal to each
other# not e"en for idea! gases (n fact# the ratio @c$>c"A of a gas is -no*n as @-A . the heat ca$acity ratio .
and it is ne"er equa! to unity This ratio is frequent!y used in gas%dynamics studies
#12.11&
0eat ca$acities can be ca!cu!ated using equations of state 1or instance# 'eng and :obinson (<IK6)
$resented an e)$ression for the de$arture entha!$y of a f!uid mi)ture# sho*n be!o*=
#12.1)&
The "a!ue of the entha!$y of the f!uid (0) is obtained by adding u$ this entha!$y of de$arture (sho*n abo"e)
to the idea! gas entha!$y (0Z) (dea! entha!$ies are so!e functions of tem$erature 1or hydrocarbons# 'assut
and Manner (<IK2) de"e!o$ed corre!ations for idea! gas $ro$erties such as entha!$y# heat ca$acity and
entro$y as a function of tem$erature Therefore# an ana!ytica! re!ationshi$ for @c$A can be deri"ed ta-ing the
deri"ati"e of (<I<2)# as sho*n be!o*=
#12.1,&
*here=
B idea! gas 3'#
a!so found in the *or- of 'assut and Manner (<IK2)
The second deri"ati"e of *ith res$ect to tem$erature can be ca!cu!ated through the e)$ression=
#12.1-a&
*here# #12.1-b&
1or the e"a!uation of e)$ression (<I<D)# the deri"ati"e of the com$ressibi!ity factor *ith res$ect to
tem$erature is a!so required Qsing the cubic "ersion of 'eng%:obinson EOS# this deri"ati"e can be *ritten
as=
#12.1.&
*here#
@c$A and @c"A "a!ues are thermodynamica!!y re!ated (t can be $ro"en that this re!ationshi$ is contro!!ed by the
'%2%T beha"ior of the substances through the re!ationshi$=
#12.1/&
1or idea! gases# and Equation (<828) co!!a$ses to=
#12.10&
(II)
:oule;4homson Coe--icient
One remar-ab!e difference bet*een f!o* of condensate (or !iquid) and natura! gases through a $i$e!ine is
that of the effect of $ressure dro$ on tem$erature changes a!ong the $i$e!ine This is es$ecia!!y true *hen
heat !osses to the en"ironment do not contro! these tem$erature "ariations +atura! gas $i$e!ines usua!!y
coo! *ith distance (effect common!y ca!!ed VLou!eSThomson coo!ing/)# *hi!e oi! !ines heat The reason for
such dissimi!arity $ertains to the different effect that $ressure dro$ has on the entro$y of a natura! gas than
on the entro$y of an oi! mi)ture Hat& (<IK2) and Hat& and 5ee (<II0) $resented a "ery en!ightening
discussion on this regard
6hether or not a gas coo!s u$on e)$ansion or com$ression . that is# *hen sub9ected to $ressure changes
. de$ends on the "a!ue of its Lou!eSThomson coefficient This is not on!y im$ortant for natura! gas $i$e!ine
f!o*# but a!so for the reco"ery of condensate from *et natura! gases (n the cryogenic industry#
turboe)$anders are used to sub9ect a *et gas to a sudden e)$ansion (shar$ $ressure dro$) in order to coo!
the gas stream beyond its de* $oint and reco"er the !iquid dro$out
Thermodynamica!!y# the Lou!eSThomson coefficient is defined as the isentha!$ic change in tem$erature in a
f!uid caused by a unitary $ressure dro$# as sho*n=
#12.11&
Qsing thermodynamic re!ationshi$s# a!ternati"e e)$ressions can be *ritten 1or e)am$!e# using the cyc!ing
ru!e *e may *rite=
#12.12&
or#
#12.)0&
#12.)1&
6e ha"e a!so seen that *e can e)$ress entha!$y changes in terms of $ressure# tem$erature and "o!ume
changes=
#12.))&
Additiona!!y# the fo!!o*ing identity can be deri"ed=
#12.),&
A!! together# *e ha"e se"era! *ays of ca!cu!ating the Lou!eSThom$son coefficient for a f!uid# as sho*n ne)t=
#12.)-&
Once the constant $ressure s$ecific heat @c$A is ca!cu!ated as discussed in the $re"ious !ecture# a!! the
entries in the $re"ious e)$ression are -no*n and the Lou!eSThomson coefficient can be ana!ytica!!y
ca!cu!ated An interesting obser"ation from a!! abo"e e)$ressions for @ A is that the Lou!eSThom$son
coefficient of an idea! gas is identica!!y equa! to &ero 0o*e"er# rea! f!uids ta-e $ositi"e or negati"e Lou!eS
Thom$son "a!ues
(II)
8iscosity
6hat other $ro$erties are *e interested in7 6e are interested in f!o* $ro$erties 6hether you are interested
in f!o* in $i$es or in $orous media# one of the most im$ortant trans$ort $ro$erties is viscosity 1!uid "iscosity
is a measure of its interna! resistance to f!o* The most common!y used unit of "iscosity is the centi%$oise#
*hich is re!ated to other units as fo!!o*s=
< c$ B 00< $oise B 00006K2 !bm>ft%s B 000< 'a%s
7atural gas viscosit* is usua!!y e)$ected to increase both *ith $ressure and tem$erature A number of
methods ha"e been de"e!o$ed to ca!cu!ate gas "iscosity The method of 5ee# 4on&a!e& and Ea-in is a
sim$!e re!ation *hich gi"es quite accurate resu!ts for ty$ica! natura! gas mi)tures *ith !o* non%hydrocarbon
content 5ee# 4on&a!e& and Ea-in (<I66) $resented the fo!!o*ing corre!ation for the ca!cu!ation of the
"iscosity of a natura! gas=
#12.).a&
*here=
#12.).b&
#12.).c&
#12.).d&
(n this e)$ression# tem$erature is gi"en in (W:)# the density of the f!uid ( ) in !bm>ft
D
(ca!cu!ated at the
$ressure and tem$erature of the system)# and the resu!ting "iscosity is e)$ressed in centi$oises (c$)
The most common!y used oil viscosit* corre!ations are those of 8eggs%:obinson and 2asque&%8eggs
3orrections must be a$$!ied for under%saturated systems and for systems *here disso!"ed gas is $resent in
the oi! 0o*e"er# in com$ositiona! simu!ation# *here both gas and condensate com$ositions are -no*n at
e"ery $oint of the reser"oir# it is customary to ca!cu!ate condensate viscosity using 5ohren&# 8ray [ 3!ar-
corre!ation 3!ar- corre!ation (t this ty$e of simu!ation# it is usua! to ca!cu!ate gas viscosities based on
5ohren&# 8ray [ 3!ar- corre!ation as *e!! This ser"es the $ur$ose of guaranteeing that the gas $hase and
condensate $hase con"erge to the same "a!ue of "iscosity as they a$$roach near%critica! conditions
5ohren&# 8ray and 3!ar- (<I6J) $ro$osed an em$irica! corre!ation for the $rediction of the "iscosity of a
!iquid hydrocarbon mi)ture from its com$osition Such e)$ression# origina!!y $ro$osed by Lossi# Stie! and
Thodos (<I62) for the $rediction of the "iscosity of dense%gas mi)tures# is gi"en be!o*=
#12.)/&
*here=
B f!uid "iscosity (c$)#
Z B "iscosity at atmos$heric $ressure (c$)#
B mi)ture "iscosity $arameter (c$
%<
)#
B reduced !iquid density (unit!ess)#
5ohrent& et al. origina! $a$er $resents a ty$ogra$hica! error in Equation (<I26) 0ere it is *ritten as
origina!!y $ro$osed by Lossi# Stie! and Thodos (<I62) A!! four $arameters !isted abo"e ha"e to be ca!cu!ated
as a function of critica! $ro$erties in order to a$$!y Equation (<I26) 5ohrent& et al. origina! $a$er uses
scientific units# here *e $resent the equi"a!ent equations in fie!d (Eng!ish) units
1or the viscosity of the mi-ture at atmospheric pressure ( Z)# 5ohrent& et al. suggested using the fo!!o*ing
0erning [ Gi$$erer equation=
#12.)0&
*here=
&9 B mo!e com$osition of the i%th com$onent in the mi)ture#
M6i B mo!ecu!ar *eight of the i%th com$onent (!bm>!bmo!)
B "iscosity of the i%th com$onent at !o* $ressure (c$)=
X if Tri \ <O Y
X if Tri F <O Y
*here=
Tri B reduced tem$erature for the i%th com$onent (T>Tci)#
M6i B "iscosity $arameter of the i%th com$onent# gi"en by=
1or the mi-ture viscosity parameter ( m)# 5ohrent& et al. a$$!ied an equi"a!ent e)$ression to that sho*n
abo"e but using $seudo%$ro$erties for the mi)ture=
#12.)1&
*here=
T$c B $seudocritica! tem$erature (
o
:)#
'$c B $seudocritica! $ressure ($sia)#
M6! B !iquid mi)ture mo!ecu!ar *eight (!bm>!bmo!)
The reduced density of the liquid mi-ture ( r) is ca!cu!ated as=
#12.)2&
*here=
B mi)ture $seudocritica! density (!bm>ft
D
)#
2$c B mi)ture $seudocritica! mo!ar "o!ume (ft
D
>!bmo!)#
A!! mi)ture $seudocritica! $ro$erties are ca!cu!ated using Hay/s mi)ing ru!e# as sho*n=
T$c B ]&iTci#12.,0a&
'$c B ]&i'ci#12.,0b&
2$c B ]&i2ci#12.,0c&
@&iA $ertains to the f!uid mo!ar com$osition# Tci is gi"en in
o
:# 'ci in $sia# and 2ci in ft
D
>!bmo! 6hen the critica!
"o!umes are -no*n in a mass basis (ft
D
>!bm)# each of them is to be mu!ti$!ied by the corres$onding
mo!ecu!ar *eight (n the case of !um$ed 3KC hea"y fractions# 5orent& et al. (<I6I) $resented a corre!ation
for the estimation 3KC critica! "o!umes
Re9erences:
5ee# A# 4on&a!e&# M# Ea-in# 8 (<I66)# @The 2iscosity of +atura! 4asesA# S'E 'a$er <DJ0# Lourna! of
'etro!eum Techno!ogy# "o! <8# $ IIK%<000
5ohren&# L# 8ray# 84# 3!ar-# 3: (<I6J)# @3a!cu!ating 2iscosities of :eser"oir 1!uids from their
com$ositionsA# S'E 'a$er I<O# Lourna! of 'etro!eum Techno!ogy# $ <<K<%<<K6
(II)
Action Item
this modu!e
Please note:
date
Problem Set
< 4as metering is a most im$ortant acti"ity in the natura! gas business Among the $ro$erties *e
ha"e studied# *hich one *ou!d you em$hasi&e in terms of accuracy for most common gas meters7
Module En*ineerin* +pplications (I)
Module Goals
Module Goal: To high!ight some of the im$ortant a$$!ications of $hase beha"ior in $roduction o$erations
Module Objective: To describe the use of f!ash ca!cu!ations in se$arator o$timi&ation and gas%
condensate reser"oir descri$tion
Introduction< Phase Behavior as the =uintessential 4ool
O$tima! design and the safe and efficient o$eration of hydrocarbon $roduction hand!ing and $rocessing
systems strong!y de$ends on accurate -no*!edge of f!uid $hase beha"ior (n fact# in contrast *ith other
disci$!ines# the $ractice of $etro!eum and natura! gas engineering centers around understanding the
interaction bet*een f!uids and "arious en"ironments# inc!uding the reser"oir# $i$e!ine# se$arator# $um$s and
com$ressors# etc Another distinguishing characteristic is the com$!e)ity of the f!uid in"o!"ed here .
$etro!eum 6hereas# for instance# mechanica! engineers dea! main!y *ith *ater (sing!e%com$onent system)
and air (considered idea! for most a$$!ications)# here *e are dea!ing *ith com$!e) hydrocarbon mi)tures
*here the com$osition de$endence of thermo$hysica! $ro$erties is "ery strong
Another com$!ication is the *ide range of $ressures and tem$eratures associated *ith the $rocesses of
interest# from u!tra!o* tem$eratures (5+4) to as much as 2<0 W1 and $ressures ranging from atmos$heric to
se"era! thousand $sia 6ithin these ranges# the f!uid can transcend the three $rinci$a! $hases# name!y gas#
!iquid# and so!id# and *orse yet# any combination of these
The combination of the com$!e) mi)tures in"o!"ed# the *ide com$ositiona! "ariabi!ity from reser"oir to
reser"oir# from system to system# and the *ide range of $ressures and tem$eratures to *hich systems are
often sub9ected (eg a $i$e!ine) ma-e the $hase beha"ior of these systems a "ery cha!!enging underta-ing
Qn!ess one has a good descri$ti"e and $redicti"e understanding of the f!uid/s $hase beha"ior# their
interactions and res$onses cannot be successfu!!y described
(n these !ast t*o modu!es of the course# *e *i!! e)amine some of the a$$!ications of our current -no*!edge
of $hase beha"ior and thermodynamics in 'etro!eum and +atura! 4as Engineering The message *e *ou!d
!i-e to $ro"ide is "ery sim$!e= the phase behavior of the hydrocarbon system must be fully grasped in order
to fu!!y understand the res$onses of condensate and natura! gas systems and o$timi&e their $erformance
1or e)am$!e# ma)imi&ation of condensate yie!d is "irtua!!y im$ossib!e *ithout the too!s for accurate
$rediction of 9ust ho* much !iquid *i!! e)ist under gi"en conditions of $ressure# tem$erature and
com$osition Therefore# ha"ing ad"anced $redicti"e too!s for the characteri&ation of hydrocarbon $hase
beha"ior *ith the highest accuracy $ossib!e is the !ey to mastering the economics of hydrocarbon systems
(n the ne)t sections# *e *i!! e)$!ore some s$ecific areas *here the mastering of $hase beha"ior conce$ts is
a must
7esi$n and ptimi>ation o- Separators
Once oi! and gas are brought to the surface# our main goa! becomes that of trans$ortion of the oi! and gas
from the *e!!head to the refinery (for fina! $rocessing) in the best possible form. A!! equi$ment and
$rocesses required to accom$!ish this are found at the surface production facility 0ence# a!! surface
$roduction starts right at the *e!!head Starting at the *e!!head# the com$!e) mi)ture of $roduced f!uids
ma-es its *ay from the $roduction tubing into the f!o* !ine +orma!!y# many *e!!s are dri!!ed to effecti"e!y
$roduce the hydrocarbons contained in the fie!d 1rom each of these *e!!s emerge one or more f!o* !ines
de$ending on ho* many !ayers are being $roduced simu!taneous!y Me$ending on the $hysica! terrain of the
area and se"era! other en"ironmenta! factors# each of the f!o* !ines may be a!!o*ed to continue from the
*e!!head to a centra! $rocessing faci!ity common!y referred as a production platform or a flow station (f not#
a!! the f!o* !ines or se"era! of them em$ty their contents into a bigger $i$e!ine ca!!ed a bul! header# *hich
then carries the f!uids to the $roduction $!atform The combination of the *e!!head# the f!o* !ines# bu!-
headers# "a!"es and fittings needed to co!!ect and trans$ort the raw $roduced f!uid to the $roduction $!atform
is referred to as the gathering system
The gathered f!uids must be $rocessed to enhance their "a!ue 1irst of a!!# f!uids must be se$arated into their
main $hasia! com$onents[mdash,name!y# oi!# *ater# and natura! gas The separation system $erforms this
function 1or this# the system is usua!!y made u$ of a free *ater -noc-%out (16HO)# f!o* !ine heater# and oi!%
gas (t*o%$hase) se$arators 6e *i!! be !oo-ing at the design of this !ast com$onent
The $hysica! se$aration of these three $hases is carried out in se"era! ste$s 6ater is se$arated first from
the hydrocarbon mi)ture (by means of the 16HO)# and then the hydrocarbon mi)ture is se$arated into t*o
hydrocarbon $hases (gas and oi!>condensate) A successfu! hydrocarbon se$aration ma)imi&es $roduction
of condensate or oi!# and enhances its $ro$erties (n fie!d a$$!ications# this is accom$!ished by means of
stage separation Stage se$aration of oi! and gas is carried out *ith a series of se$arators o$erating at
consecuti"e!y reduced $ressures 5iquid is discharged from a higher%$ressure se$arator into the ne)t%!o*er%
$ressure se$arator The $ur$ose of stage se$aration is to obtain ma)imum reco"ery of !iquid hydrocarbons
from the f!uids coming from the *e!!heads and to $ro"ide ma)imum stabi!i&ation of both the !iquid and gas
eff!uents
ur9ace +roduction Facilit*: The $hysica! insta!!ation *here f!uids coming from the *e!!head are
se$arated into three main constituents= *ater# oi!# and natura! gas
Figure )0.1: +urpose o9 a ur9ace +roduction Facilit*

Qsua!!y it is most economica! to use three to four stages of se$aration for the hydrocarbon mi)ture 1i"e or
si) may $ayout under fa"orab!e conditions# *hen . for e)am$!e . the incoming *e!!head f!uid is found at
"ery high $ressure 0o*e"er# the increase in !iquid yie!d *ith the addition of ne* stages is not linear. 1or
instance# the increase in !iquids gained by adding one stage to a sing!e%stage system is !i-e!y to be
substantia! 0o*e"er# adding one stage to a three or four stage system is not as !i-e!y to $roduce any ma9or
significant gain (n genera!# it has been found that a three stage se$arating system is the most cost effecti"e
1igure 202 sho*s this ty$ica! configuration
Figure )0.): $!ree8stage ur9ace eparation Facilit*

Qnder the assum$tion of equi!ibrium conditions# and -no*ing the com$osition of the f!uid stream coming into
the se$arator and the *or-ing $ressure and tem$erature conditions# *e cou!d a$$!y our current -no*!edge
of 25E equi!ibrium (f!ash ca!cu!ations) and ca!cu!ate the "a$or and !iquid fractions at each stage 0o*e"er# if
*e are !oo-ing at designing and o$timi&ing the se$aration faci!ity# *e *ou!d !i-e to -no* the o$tima!
conditions of $ressure and tem$erature under *hich *e *ou!d get the most economica! $rofit from the
o$eration (n this conte)t# *e ha"e to -ee$ in mind that stage se$aration aims at reducing the $ressure of
the $roduced f!uid in sequentia! ste$s so that better and more stoc-%tan- oi!>condensate reco"ery *i!! resu!t
Se$arator ca!cu!ations are basica!!y $erformed to determine=
O$timum se$aration conditions= se$arator $ressure and tem$erature
3om$ositions of the se$arated gas and oi! $hases
Oi! formation "o!ume factor
'roducing 4as%Oi! ratio
A'( gra"ity of the stoc- tan- oi!
5et us !oo- at the case of three%stage se$aration (n genera!# tem$erature conditions in the surface
se$aration faci!ity are "ery much determined by the atmos$heric condition and incoming stream
tem$eratures As for $ressures# the "ery first se$arator $ressure is contro!!ed by the gathering !ines coming
from *e!! heads# thus there is not much room for $!aying *ith $ressure in the first se$arator The same
arguments are "a!id for the !ast stage of se$aration (stoc- tan-)# *hich usua!!y o$erates at atmos$heric
conditions Therefore# *e are on!y !eft *ith the middle separator for o$timi&ation
As it turns out# the -ey to designing a three stage se$aration system is finding the optimum pressure at
*hich to o$erate the second se$arator The question that *e *ou!d ans*er is @*hat is the $ressure that *i!!
resu!t in the best qua!ity !iquid going out of the stoc- tan- for sa!es7A 6e do not *ant to do this em$irica!!y
This is# *e do not *ant to $!ay *ith the second stage se$arator $ressure in the fie!d# unti! *e u!timate!y find
the o$timum condition 6hat *e can do# using our $hase beha"ior -no*!edge# is to find this o$timum midd!e
stage $ressure a$$!ying our understanding of 25E equi!ibrium
1igure 20D sho*s the ty$ica! effect of $!aying *ith the midd!e se$arator $ressure on the qua!ity and quantity
of $roduced oi!>condensate at the stoc- tan- Tua!ity and quantity are measured in terms of $ro$erties# such
as A'( and 8o# and the o"era!! 4O: at the se$aration faci!ity
Figure )0.,: election o9 Opti"u" Middle eparator +ressure
The o$timum "a!ue of $ressure for the midd!e stage is the one that $roduces the ma)imum !iquid yie!d (by
minimi&ing 4O: and 8o) of a ma)imum qua!ity (by ma)imi&ing stoc-%tan- A'( gra"ity) The sma!!er the "a!ue
of 4O: and 8o# the !arger the !iquid yie!d The higher the A'( gra"ity of the stoc-%tan- f!uid# the more
$rofitab!e its commercia!i&ation 1rom 1igure 202# *e see that this condition is found at neither e)treme
(!o*>high) "a!ues of midd!e stage $ressure There is# in fact# an o$tima! "a!ue for midd!e stage $ressure This
is the "a!ue *e are !oo-ing for
The 'hase 8eha"ior mode! that *e ha"e described throughout these series of !ectures $ro"ides the basic
frame*or- for the ty$e of ca!cu!ations required here Additiona!!y# *e discussed ho* A'( and 8o can be
ca!cu!ated using the out$ut of the $hase beha"ior mode! 6hi!e doing the ca!cu!ations for a D%stage
se$arating system# -ee$ in mind that *e ha"e minima! contro! o"er feed $ressure# as *e do not *ant to
inhibit the *e!! (high%$ressure se$arator) 6e do not contro! the sa!es !ine $ressure (stoc-%tan- $ressure)
either The contro! that *e do ha"e is the o$erating $ressure of the midd!e se$arator
:eca!! that finding the o$timum $ressure ca!!s for# in $art# finding the minimum gas to oi! ratio (4O:#
S31>ST8) 6e are dea!ing# in this case# *ith tota! 4O: The tota! 4O: is the cumu!ati"e amount of gas
from a!! three se$arators di"ided by the amount of !iquid>condensate !ea"ing the stoc- tan- Muring our
discussion on 8o%ca!cu!ations# *e ca!!ed @nstA the mo!es of !iquid !ea"ing the stoc- tan- $er mo!e of feed
entering the se$aration faci!ity This number can be obtained by sequentia!!y f!ashing < !bmo! of feed through
each of the se$aration stages :eca!!ing the definition of 4O:#
#)0.1&
*here=
Xbasis= < !bmo! of feedY
Therefore#
XS31>ST8Y#)0.)&
Qsua!!y# the stoc- tan- is considered to o$erate at standard conditions ($sc# Tsc) +o* you are ready to ma-e
your o*n surface se$aration design^
Compositional Modelin$ o- Gas!Condensate Reservoirs< 4he 0ero!
dimensional Approach
'hase beha"ior is re!e"ant to e"ery as$ect of $etro!eum and natura! gas engineering According to the
com$!e)ity of the reser"oir f!uid $hase beha"ior# reservoir modeling is c!assified under t*o distinct grou$s=
b!ac-%oi! simu!ation and com$ositiona! simu!ation Often times# it is safe to assume that reser"oir f!uid
beha"ior is on!y a function of $ressure and inde$endent of com$osition This sim$!ified beha"ior is ty$ica! of
@b!ac-%oi!A systems (n this case# reser"oir hydrocarbon f!uids are assumed to be com$rised of t*o
com$onents# name!y oi! and gas The mode! a!!o*s for certain amount of gas to be in so!ution *ith the oi! at
reser"oir conditions The amount of disso!"ed gas increases *ith# and is a so!e function of# $ressure for
conditions be!o* the bubb!e $oint Abo"e the bubb!e $oint $ressure# the oi!%com$onent carries a!! the
a"ai!ab!e gas in the reser"oir# and a @"ariab!e bubb!e $ointA a!gorithm is usua!!y im$!emented to $redict
conditions for the re!ease of the disso!"ed gas 1or this @b!ac-%oi!A sim$!ified mode! to be "a!id# actua! oi! and
gas $hases shou!d maintain a fi)ed%com$osition throughout the $rocess simu!ated in the reser"oir (n certain
cases# the assum$tion of fi)ed oi! and gas com$osition is no !onger "a!id= for instance# de$!etion of gas%
condensate reser"oirs and "o!ati!e%oi! reser"oirs# and $rocesses that aim at the "a$ori&ation or miscib!e
f!ooding of the in%situ f!uids by f!uid in9ection More com$!e) f!uid beha"ior requires treating a!! hydrocarbon
$hases as nc%com$onent mi)tures and thus $erforming a @com$ositiona! simu!ationA
A!though the need for ta-ing com$ositiona! de$endence of thermodynamic and hydrodynamic $arameters
into account in reser"oir descri$tion has been recogni&ed for a !ong time# the actua! im$!ementation has not
been rea!i&ed unti! re!ati"e!y recent!y One of the main reasons is due to the !ac- of sim$!e and re!iab!e
methods of $redicting $hase beha"ior under the conditions of interest T*o things ha"e ha$$ened *ithin the
!ast three decades that ha"e changed the situation= They are (<) the a"ai!abi!ity of fast and re!ati"e!y
ine)$ensi"e com$utationa! $o*er to carry out the great number of ca!cu!ations in"o!"ed and (2) the
de"e!o$ment of sam$!es and fair!y good equations of state
Sim$!y $ut# a com$ositiona! reser"oir simu!ator is a dynamic integration of the f!uid dynamic $orous media
mode! and the $hase beha"ior mode!# neither of *hich is subordinated to the other (n fact# in the ear!y days
of com$ositiona! reser"oir simu!ation# a non%dynamic integration of these t*o *as the norm The more
recent mode!s actua!!y attem$t a fu!! dynamic integration The need for integration had been recogni&ed
ear!ier $articu!ar!y for gas condensate reser"oir# gas cyc!ing $rocesses# and "o!ati!e oi! systems
Ear!y de"e!o$ments in reser"oir engineering ana!ysis re!ied on &ero%dimensiona! or tan- materia! ba!ances
for the e"a!uation and forecasting of reser"oir $erformance (n <ID6# Schi!thuis de"ised *hat *e no* regard
as the c!assica! materia! ba!ance equation Schi!thuis%ty$e materia! ba!ances are on!y "a!id for b!ac-%oi!
systems and are not a$$!icab!e for reser"oir f!uids *ith com$!e) beha"ior such as gas condensates and
"o!ati!e oi!s 3om$ositiona! considerations *ere incor$orated into &ero%dimensiona! mode!ing in the decade
of <IO0/s *ith the *or-s of A!!en and :o* (<IO0)# 8rin-man and 6einaug (<IOK)# :eude!huber and 0inds
(<IOK)# Lacoby and 8erry (<IOK)# and Lacoby et al. (<IOI) These can be regarded as the first generation of
com$ositiona! simu!ators E"en though &ero%dimensiona! simu!ations ha"e been !arge!y o"erthro*n by more
so$histicated numerica! simu!ation techniques# they are sti!! considered the most sim$!e and fundamenta!
too! a"ai!ab!e for the ana!ysis of reser"oir $erformance
The &ero%dimensiona! mode!s ma-e t*o $rinci$a! assum$tions The first is to basica!!y ignore the t*o%*ay
cou$!ing bet*een f!uid/s thermo$hysica! $ro$erties and the hydrodynamic characteristics The reser"oir is
treated as a $erfect!y mi)ed tan- reactor *ith uniform $ro$erties 6e assume no dimensions# and that one
sing!e "a!ue of $ressure and tem$erature describes the a"erage beha"ior of the entire reser"oir The second
assum$tion is to neg!ect the hydrodynamic interactions bet*een the f!o*ing gas and !iquid $hases (n other
*ords# the &ero%dimensiona! com$ositiona! mode! re!ies on phase behavior as the most crucia! effect
contro!!ing the descri$tion of reco"ery $erformance
There is no doubt that significant insights# albeit qua!itati"e# are $ro"ided by these studies Gero%dimensiona!
mode!ing $ro"ides a !ess e)$ensi"e too! for the engineer to gain some insight into the e)$ected $erformance
of a gas condensate reser"oir under de$!etion Sometimes *e s$end a great dea! of time dea!ing *ith the
numerics of the dimensiona! com$ositiona! simu!ators# and *e may forget that phase behavior is the sing!e
most im$ortant constituent of the de$!etion $erformance of# for instance# gas%condensate systems
+e"erthe!ess# the reser"oir engineer must -ee$ in mind that this ty$e of ana!ysis does not $ro"ide the most
accurate reser"oir descri$tion 1or instance# the effect of heterogeneities on reser"oir $erformance cannot
be studied *ith a &ero%dimensiona! mode! Again# the goa! is to ta-e a !oo- at the qua!itati"e insights that
f!uid '2T beha"ior can $ro"ide us
The ty$ica! de$!etion sequence that a &ero%dimensiona! com$ositiona! simu!ator fo!!o*s is described be!o*
This c!assica! ana!ysis treats gas condensate $erformance as constant "o!ume de$!etion (32M) in a '2T
ce!! The u!timate out$ut of the mode! is basica!!y com$rised of 4O: $rediction and the com$ositions of the
gas and condensate surface eff!uents 6e start *ith a sing!e%$hase gas reser"oir f!uid# of a -no*n
com$osition# at an initia! reser"oir $ressure and tem$erature 6e f!ash this f!uid se"era! times through a
series of $ressure de$!etion stages unti! abandonment conditions are found :eser"oir "o!ume is -e$t
constant throughout the de$!etion $rocess
The ty$ica! de$!etion sequence that a &ero%dimensiona! com$ositiona! simu!ator fo!!o*s are !isted be!o*=
< 3a!cu!ate the density and mo!ecu!ar *eight of the initia! reser"oir f!uid 6ith this information# and
-no*ing the initia! reser"oir "o!ume (2ti)# ca!cu!ate the initia! amount of gas in $!ace (!bmo!s) An
a!ternati"e a$$roach is to start *ith a fi)ed amount of !bmo!s of reser"oir f!uid# and ca!cu!ate the
corres$onding initia! reser"oir "o!ume (2ti) 6e assume a "o!umetric reser"oir and thus the initia!
reser"oir "o!ume (2ti) is -e$t constant throughout the ca!cu!ations
2 Qsing the reser"oir f!uid com$osition# distribute the initia! mo!es of reser"oir f!uids into com$onents#
and store such quantities for materia! ba!ance accounting
D .epletion step: 5o*er the reser"oir $ressure by a gi"en amount (ty$ica!!y# 200 $si) 1!ash the
reser"oir f!uid at the ne* $ressure# ca!cu!ate amount of mo!es in the gas and !iquid $hases (@4asTA
and @5iqTA) and the densities and mo!ecu!ar *eights of each of the $hases at the ne* condition
J /-pansion: 6ith mo!ecu!ar *eight# density# and tota! mo!ar amount of each of the $hases# ca!cu!ate
the ne* tota! "o!ume that the f!uids occu$y at the ne* condition (2e)$)
O 3a!cu!ate the e-cess "o!ume of f!uids# ta-ing the difference bet*een the ne* "o!ume u$on
e)$ansion (2e)$) and the reser"oir "o!ume (2ti) This re$resents the "o!ume of f!uid that must ha"e
been *ithdra*n by the *e!! in order to reach the ne*!y im$osed $ressure condition# ie
2*s B 2e)$ S 2ti#)0.,&
6 3a!cu!ate the $ercentage of !iquid in the *e!! stream using mobi!ity ratio considerations Tria! and
error $rocedure is necessary for the !iquid accounting The tota! amount of !iquid a"ai!ab!e u$on
de$!etion (5iqT) must be distributed bet*een the *e!!stream (5iq6S) and the !iquid remaining in the
reser"oir (5iq:) Additiona!!y# the mo!es of reser"oir !iquid @5iq:A can be e)$ressed in terms of
oi!>condensate saturation Oi! saturations define the mobi!ity of the gas and !iquid $hases These
interre!ations are sho*n be!o*=
5iqT B 5iq6S C 5iq:#)0.-a&
#)0.-b&
, , , Sg B < % So#)0.-c&
#)0.-d&
5iq6S is a function of mobi!ity ratio# *hich is a function of 5iq: (through So) As a first guess# ta-e
5iq: B 5iqT and ca!cu!ate the corres$onding 5iq6S Ma-e ne* guesses (decreasing the "a!ue in
e"ery ne* tria!) unti! the !iquid ba!ance in Equation (20Ja) is satisfied
K Once 5iq6S and (2*s)!iq are -no*n# obtain the tota! "o!ume of gas *ithdra*n from the reser"oir by
subtracting the !iquid "o!ume (2*s)!iq from the tota! *e!!stream "o!ume (2*s) E)$ress this gas "o!ume
in mo!es using reser"oir gas density and mo!ecu!ar *eight 3a!cu!ate the tota! number of mo!es of
the *e!!stream
8 Materia! 8a!ance Accounting= 3a!cu!ate the number of mo!es of each com$onent remaining in the
reser"oir To do this= subtract the number of mo!es !ea"ing the *e!! stream from the number in the
reser"oir before f!ashing for each of the com$onents 3a!cu!ate the ne* o"era!! com$osition of the
reser"oir f!uid
I 3a!cu!ate the o"era!! com$osition of the $roduced *e!! stream# by mi)ing the com$osition of gas
and !iquid coming a!ong
<0 0urface Production Facility: 1!ash the incoming *e!!stream com$osition through the train of
se$arations 3a!cu!ate the tota! amount of gas and !iquid !ea"ing the se$aration faci!ity and 4O:
3a!cu!ate the $ercentage of reco"ery from the reser"oir
<< A de$!etion !oo$ has been com$!eted 4o bac- to ste$ D unti! abandonment $ressure is reached
(ty$ica!!y# 600 $sia)
<2 '!ot !iquid $roduction# gas $roduction# 4O:# and reco"ery from the reser"oir as a function of
$ressure de$!etion# from initia! reser"oir conditions to abandonment conditions
The basic 25E ca!cu!ations required here can be $erformed using the 'eng%:obinson EOS and equi!ibrium
considerations 5iquid "iscosities can be ca!cu!ated through the 5ohren&# 8ray# and 3!ar- corre!ation# and
gas "iscosities can be ca!cu!ated using the 5ee%4on&a!e& corre!ation 1!uid densities are obtained direct!y
through the 'eng%:obinson EOS
Action Item
for this modu!e
Please note:
date
Problem Set
< A'(# 4O: and 8o are the $arameters that *e use to o$timi&e a train of se$arators S$ecu!ate on
*hy a!! three $arameters seem to $redict the same o$tima! se$arator $ressure
2 A!though &ero%dimensiona! mode!ing can be used to mode! beha"ior of gas%condensate systems#
there are some $itfa!!s in the descri$tion 6hat are these $itfa!!s7 (n *hat cases can *e o"er!oo-
them7
Module En*ineerin* +pplications (II)
Module vervie#
Module Goal: To high!ight some of the im$ortant a$$!ications of $hase beha"ior in $roduction o$erations
Module Objective: To high!ight the use of $hase beha"ior for the descri$tion of gas $i$e!ines# gas
metering and hydrate systems
?atural Gas Pipeline Modelin$
Once natura! gas is $roduced and $rocessed# fe* to se"era! hundred mi!es may !ie in bet*een it and its fina!
consumers A cost%effecti"e means of trans$ort is essentia! to bridge the ga$ bet*een the $roducer and
consumer (n the techno!ogica! arena# one of the cha!!enges $ertains to the ca$acity of the industry to ensure
continuous de!i"ery of natura! gas *hi!e its demand is steadi!y increasing Thus# it is no *onder that
$i$e!ines ha"e become the most $o$u!ar means of trans$orting natura! gas from the *e!!head to $rocessing
. and from there to the fina! consumer . since it better guarantees continuous de!i"ery and assures !o*er
maintenance costs
'hase 8eha"ior ('%2%T data) is crucia! for a!! our engineering designs Accurate $rediction of the '%2%T
$ro$erties of natura! gases is es$ecia!!y critica! *hen dea!ing *ith $i$e!ine design# gas storage# and gas
measurement 6hi!e describing natura! gas $i$e!ine design# it is necessary to distinguish bet*een t*o
cases= the design of $i$e!ines for trans$ortation of regu!ar dry gases (no !iquid# sing!e%$hase trans$ortation)
and the design of $i$e!ines for trans$ortation of *etter gases . *here mu!ti$hase conditions due to
condensate dro$out may are $ossib!e
The ma9or "ariab!es that affect the design of gas $i$e!ines are= the $ro9ected "o!umes that *i!! be
trans$orted# the required de!i"ery $ressure (sub9ect to the requirements of the faci!ities at the consumer
end)# the estimated !osses due to friction# and the e!e"ation changes im$osed by the terrain to$ogra$hy
O"ercoming such !osses *i!! !i-e!y require higher $ressure than the one a"ai!ab!e *hen the gas is being
$roduced Thus# forcing a gi"en gas rate to $ass through a $i$e!ine *i!! ine"itab!y require the use of
com$ressor stations
5oss in mechanica! energy resu!ts from mo"ing f!uids through $i$e!ines Energy !osses in a $i$e!ine can be
trac-ed by "irtue of the $ressure and tem$erature changes e)$erienced by the f!o*ing stream Mesign
equations re!ate $i$e!ine $ressure dro$ *ith the gas f!o* rate being trans$orted The fo!!o*ing is the genera!
equation for a sing!e%$hase gas $i$e!ine f!o* in steady state=
#)1.1&
+ote that f!o* rate is $ro$ortiona! to the in"erse square root of com$ressibi!ity (G) 1or near%idea! conditions#
the effect of com$ressibi!ity on f!o* rate is !i-e!y to be sma!! 8ut for high%$ressure f!o*s# G may de"iate
great!y from < Qnder these conditions# inaccuracy in the $rediction of G may !ead to a substantia! error in
the ca!cu!ated f!o* rate and thus a com$!ete!y *rong $i$e!ine si&ing for design $ur$oses
Once a $i$e!ine is de$!oyed# it has a more or !ess a fi)ed o$erationa! region An u$$er and !o*er set of
o$erationa! conditions a!!o*ab!e *ithin the $i$e!ine (in terms of $ressure and tem$erature) *i!! e)ist On the
one hand# the u$$er a!!o*ab!e condition *i!! be set by the $i$e strength# $i$e materia!# diameter# and
thic-ness These *i!! dictate the ma)imum $ressure that the $i$e can endure *ithout fai!ure (ie# ma)imum
o$erating $ressure) On the other hand# ma)imum $ressure and tem$erature of the com$ressor station
discharge (*hich feeds the in!et of the $i$e) *i!! a!so contribute to set this u$$er !e"e! (t is c!ear that the
conditions at the discharge of the com$ressor station cannot go beyond the ma)imum o$erating $ressure of
the $i$e . other*ise the $i$e *i!! fai! The minimum or !o*er $ressure and tem$erature condition of the
o$erationa! region *i!! be assigned by contractua! agreement *ith the end consumer The foregoing
descri$tion of the o$erationa! region is sho*n schematica!!y as the shaded area in 1igure 2<<
Figure )1.1: +ipeline operational curve and transported gas p!ase envelope
(n natura! gas f!o*# $ressure and tem$erature changes ('%T trace) may cause formation of a !iquid $hase
o*ing to $artia! condensation of the gaseous medium :etrograde $henomenon . ty$ica!!y found in mu!ti%
com$onent hydrocarbon systems . ta-es $!ace by a!!o*ing condensation of the gas $hase and !iquid
a$$earance e"en under e)$ansion of the f!o*ing stream The same $henomenon may a!so cause
"a$ori&ation of the !iquid $hase such that it reenters the gas $hase 5iquid and gas $hase com$osition are
continuous!y changing throughout the $i$e due to the unceasing mass transfer bet*een the $hases (n
genera!# the amount of hea"ies in the stream determines the e)tent of the retrograde beha"ior and !iquid
a$$earance 1igure 2<< sho*s a '%T trace or o$erationa! cur"e for a gi"en $i$e!ine# *hich is a!*ays found
*ithin the $i$e!ine o$erationa! region
1igure 2<< a!so sho*s four ty$ica! $hase en"e!o$es for natura! gases# *hich differ in the e)tent of their
hea"y com$onents 1or a gi"en com$osition# the $re"ai!ing $ressure and tem$erature conditions *i!!
determine if the f!uid state is a!! !iquid (sing!e%$hase)# a!! gas (sing!e%$hase) or gas%!iquid (t*o%$hase) Each
en"e!o$e re$resents a thermodynamic boundary se$arating the t*o%$hase conditions (inside the en"e!o$e)
from the sing!e%$hase region (outside) Each en"e!o$e is made of t*o cur"es= the de* $oint cur"e (right
arm# *here the transition from t*o%$hase to sing!e%gas occurs) and the bubb!e $oint cur"e (!eft arm# *here
the transition from sing!e%!iquid to t*o%$hase occurs) 8oth arms meet at the critica! $oint# *hich is sho*n in
1igure 2<< The *etness of the gas is an im$ortant conce$t that he!$s to e)$!ain the different features
$resented in 1igure 2<< This conce$t $ertains to the amount of hea"y hydrocarbons (high mo!ecu!ar
*eight) that are $resent in the gas com$osition (n 1igure 2<<# the driest gas . ie# the !east *et . can be
recogni&ed as that *hose !eft and right arms are the c!osest to each other# ha"ing the sma!!est t*o%$hase
region (gas A) (n this figure# it can be seen that the right arm is e)treme!y susce$tib!e to the $resence of
hea"ies in the natura! gas com$osition Me$ending on the gas com$osition# the $i$e!ine o$erationa! region
can be either com$!ete!y free of !iquid (gas A# the driest) or $artia!!y submerged in the t*o%$hase region (gas
8# 3) (f the gas is *et enough# the $i$e!ine *i!! be entire!y sub9ected to t*o%$hase conditions (gas M# the
*ettest) One may describe the sensiti"ity of the right arm to hea"ies as ha"ing a hoo-%sei&ing effect= the
!arger the e)tent of hea"ies in the natura! gas# the more the Vhoo-/ is ab!e to sei&e $art of the $i$e!ine
o$erationa! region (n conc!usion# since the o$erationa! region is more or !ess gi"en by contractua! and
design considerations# the !iquid $resence in a $i$e!ine is u!timate!y dictated by the $ro$erties of the gas that
is being trans$orted
(n the $receding figure# a $i$e!ine hand!ing a dry gas (gas A) *i!! be o$erating a sing!e%$hase mode from its
in!et through its out!et 1or this case# any of the $o$u!ar sing!e%$hase gas equations (6eymouth# 'anhand!e
ty$e# A4A equation) can be used for design $ur$oses and to he!$ to $redict the actua! o$erationa! cur"e ('%
T trace) (f a richer gas comes into the system (gas 3)# it *i!! sho* a sing!e%$hase condition at the in!et# but
after a certain distance the $ressure and tem$erature conditions *i!! be *ithin the t*o%$hase region The
case might a!so be that the system is trans$orting a *etter gas (gas M)# in *hich case it *ou!d encounter
t*o%$hase conditions both at the in!et and at the out!et of the $i$e
'enn State has de"oted a great dea! of effort in the de"e!o$ment of t*o%f!uid mode!s for the descri$tion of
mu!ti%$hase f!o* condition in natura! gas $i$e!ines (n this a$$roach# mass# momentum# and energy
equations are so!"ed simu!taneous!y Some sim$!ifying assum$tions are made based on engineering
9udgment 1or instance# the -no*!edge of a"eraged f!o* fie!d characteristics and f!uid $ro$erties at e"ery
$oint of the $i$e!ine is usua!!y more meaningfu! than a detai!ed $rofi!e of the said $ro$erties *ithin the cross
section 0ence# genera!!y s$ea-ing# the t*o%f!uid mode! a!*ays dea!s *ith conser"ation equations *ritten
on!y in one dimension for $i$e!ine f!o* (the direction of the f!o* a!ong the $i$e)# em$!oying cross%sectiona!%
a"eraged "a!ues for each term The use of a"eraged quantities absorbs the "ariations across the $i$e
section 'ressures and tem$eratures are assumed to be the same in both $hases at any gi"en $oint of the
$i$e Additiona!!y# since the main interest is to focus on norma! o$eration conditions# the further sim$!ification
of steady state conditions is in"o-ed
As *e ha"e discussed# $hase beha"ior is a crucia! com$onent in $i$e!ine design +ot on!y because *e need
to account for gas "o!umetric beha"ior in the design equations (through# for instance# G%factor ca!cu!ations)#
but a!so because it $ro"ides a means for $redicting *hether mu!ti%$hase f!o* conditions are to be found
5iquid a$$earance in natura! gas $i$e!ines is as undesirab!e as it is ine"itab!e On one side# the f!uid $hase
beha"ior and $re"ai!ing conditions ma-e it ine"itab!e On the other# the condensate sub9ects the gas $i$e to
an increasing and undesirab!e energy !oss Thus# a $ro$er $i$e!ine design must account for the effect of
condensate formation on the $erformance of the gas !ine
4he 9ydrate Problem
+atura! gas hydrates are so!id crysta!!ine com$ounds of sno* a$$earance *ith densities sma!!er than that of
ice +atura! gas hydrates are formed *hen natura! gas com$onents# for instance methane# ethane# $ro$ane#
isobutene# hydrogen su!fide# carbon dio)ide# and nitrogen# occu$y em$ty !attice $ositions in the *ater
structure (n this case# it seems !i-e *ater so!idifying at tem$eratures considerab!y higher than the free&ing
$oint of *ater
4as hydrates constitute a so!id so!ution.gas being the so!ute and *ater the so!"ent.*here the t*o main
constituents are not chemica!!y bounded 1igure 2<2 $resents a ty$ica! $hase diagram for a mi)ture of
*ater *ith a !ight# $ure hydrocarbon (03)# simi!ar to that $resented by Mc3ain (<II0)
Figure )1.): +!ase >iagra" 9or a <ater?@*drocarbon #@C& *ste"
There are a number of $oints on the diagram in 1igure 2<2 that are note*orthy 1irst of a!!# hydrate
formation is c!ear!y fa"ored by !o* tem$erature and high $ressure The three1phase critical point is $oint 3
on the diagram that re$resents the condition *here the !iquid and gas hydrocarbon merge into a sing!e
hydrocarbon $hase in equi!ibrium *ith !iquid *ater 'oint T2 is the upper quadruple point# *here four $hases
(!iquid *ater# !iquid hydrocarbon# gaseous hydrocarbon# and so!id hydrate) are found in equi!ibrium 'oint T<#
the lower quadruple point# ty$ica!!y occurs at D2 W1 (ice free&ing $oint) *here four $hases (ice# hydrate#
!iquid *ater# and hydrocarbon gas) are found in equi!ibrium (n this conte)t# $hases are not $ure as they
contain some amount of the other substances according to their mutua! so!ubi!ity
1or $ractica! a$$!ications# the most im$ortant equi!ibrium !ine is the T<T2 segment (t re$resents the
conditions for hydrate formation or dissociation# a critica! $iece of information for most industria! a$$!ications
*here hydrates are in"o!"ed 6hen *e focus on this &one# the $hase beha"ior of *ater>hydrocarbon system
is sim$!ified to the schematics sho*n in 1igure 2<D
Figure )1.,: +!ase Ae!avior o9 <ater?@*drocarbon *ste" #Q1Q) seg"ent&
'hase 8eha"ior thermodynamics is usua!!y in"o-ed for the $rediction of the T<T2 hydrate
formation>dissociation !ine The first t*o methods of $rediction *ere $ro$osed by Hat& and co*or-ers# and
are -no*n as the 4as 4ra"ity Method (Hat&# <IJO) and the Hi%"a!ue Method (3arson and Hat&# <IJ2) 8oth
methods a!!o* ca!cu!ating the '%T equi!ibrium cur"es for three $hases= !iquid *ater# hydrate and natura! gas
These methods yie!d initia! estimates for the ca!cu!ation and $ro"ide qua!itati"e understanding of the
equi!ibrium, the !atter method being the more accurate of the t*o The third method re!ies on Statistica!
Mechanics for the $rediction of equi!ibrium (t is recogni&ed as the most accurate of a!! three%$hase
ca!cu!ations as it is more com$rehensi"e and detai!ed
The -ey circumstances that are essentia! for hydrate formation can be summari&ed as=
< +resence o9 B9reeC 4ater +o hydrate formation is $ossib!e if @freeA *ater is not $resent 0ere# *e
understand the im$ortance of remo"a! of *ater "a$or from natura! gas# so that in case of free *ater
occurrence there is !i-e!ihood of hydrate formation
2 Do4 te"peratures# at or be!o* the hydrate formation tem$erature for a gi"en $ressure and gas
com$osition
D @ig! operating pressures.
J @ig! velocities; or agitation; or pressure pulsations# in other *ords turbu!ence can ser"e as
cata!yst
O +resence o9 @) and CO) $romotes hydrate formation because both these acid gases are more
so!ub!e in *ater than the hydrocarbons
The best and $ermanent remedy for the hydrate formation $rob!ems is the dehydration of the gas
Sometimes# it is quite $ossib!e that hydrates *i!! form at the *e!! site or in the $i$e!ine carrying natura! gas to
the dehydration unit# so that the need for *e!! head techniques arises At *e!! site# t*o techniques are
a$$ro$riate=
< 0eating the gas stream and maintaining f!o* !ines and equi$ment at tem$erature abo"e the
hydrate $oint#
2 (n cases *here !iquid *ater is $resent and the f!o*!ines and equi$ment cannot be maintained
abo"e hydrate tem$erature# inhibiting hydrate formation by in9ecting additi"es that de$ress both
hydrate and free&ing tem$eratures
The most common additi"es are methano!# ethy!ene g!yco!# and diethy!ene g!yco! Methano! in9ection is "ery
beneficia! in cases *here a !o* gas "o!ume does not $ermit the dehydration $rocessing (t is a!so e)treme!y
usefu! in cases *here hydrate $rob!ems are re!ati"e!y mi!d# infrequent# or $eriodic# in cases *here inhibitor
in9ection is on!y a tem$orary $hase in the fie!d de"e!o$ment $rogram# or *here inhibition is done in
con9unction *ith a $rimary dehydration system
Gas Meterin$
4as measurement is another area of hydrocarbon engineering *here accurate $rediction of the '%2%T
$ro$erties of the *or-ing f!uid is es$ecia!!y critica! One of the most *ide!y used meters used in the
measurement of gas f!o* is the orifice meter Orifice meters are c!assified as inferential meters because the
gas "o!ume is ca!cu!ated from readings of $ressure "ariation as the gas $asses through an orifice# and it is
not obtained by a direct reading
The orifice meter is arranged so that the f!o*ing gas is constricted at a $articu!ar !ocation by a thin orifice
$!ate "ery accurate!y gauged and ca!ibrated so as to be in a concentric $osition in the $i$e The reduction of
the cross section of the f!o*ing gas stream in $assing through the orifice increases the "e!ocity head at the
e)$ense of the $ressure head# and the reduction in $ressure bet*een the ta$s is measured by manometers
(or a recording meter) A ty$ica! orifice meter is sho*n in 1igure 2<J
Figure )1.-. Ori9ice Meter
Among the ad"antages of using oriface meters for gas measurement $ur$oses are the fo!!o*ing facts=
They are sim$!e in design and ha"e no mo"ing $arts
They are re!ati"e!y accurate
They are easy to insta!! and maintain
They co"er a *ide range of ca$acity
They re$resent a !o* cost
There is a great dea! of e)$erience in their use
Among the disad"antages of oriface meters are the fo!!o*ing facts=
They re$resent an intrusi"e measurement technique and a f!o* restriction that trans!ates into a
!arge energy !oss
The orifice ho!e can be eroded by sand or corrosi"e f!uids
The ho!e may be obstructed by *a) or hydrate
Among the ad"antages of using orifice meters for gas measurement $ur$oses are the fact that they are
sim$!e in design and ha"e no mo"ing $arts# re!ati"e!y accurate# easy to insta!! and maintain# co"er a *ide
range of ca$acity# re$resent a !o* cost# and there is a great dea! of e)$erience in their use Among the
disad"antages of orifice meters# are the fact that they re$resent an intrusi"e measurement technique and a
f!o* restriction that trans!ates into a !arge energy !oss# the orifice ho!e can be eroded by sand or corrosi"e
f!uids# and the ho!e may be obstructed by *a) or hydrate
8ernou!!i/s equation is then used as the basis for corre!ating the increase in "e!ocity head *ith the decrease
in $ressure head (n the ca!cu!ation of gas f!o* rate using an orifice meter# t*o quantities must be measured=
the static $ressure (ie the !ine $ressure) and the differentia! $ressure (ie the $ressure dro$ across the
orifice $!ate) The fo!!o*ing is the basic equation for gas f!o* through an orifice meter=
#)1.)&
(n Equation (2<2)# f!o* rate is a function of gas com$ressibi!ity factor (G) Again# for high%$ressure f!o*s# an
error in the com$ressibi!ity factor cou!d resu!t in an erroneous!y ca!cu!ated f!o* rate (f you ha"e some error
on G%factor# this automatica!!y trans!ates into error in the gas meter Accurate $hase beha"ior $rediction
techniques are a must in gas metering
(n the +atura! 4as (ndustry# the $oint of gas e)change bet*een the buyer and the se!!er is ca!!ed custody
transfer Muring custody transfer o$erations# accurate measurements of the quantity and qua!ity of the
e)changed gas are of crucia! im$ortance because of its economica! im$!ications Economic transactions are
based on "o!umetric rate measurements# *hich are regu!ated to be made at the same base conditions
(ndustry base conditions or standard conditions (S3) are usua!!y ta-en as ' B <JK $sia and T B 600 W1 A
!o* $ercent inaccuracy in the G%factor ca!cu!ation of a gas in transfer can easi!y trans!ate into thousands of
do!!ars of !osses on a dai!y basis^ (n fact# f!o* rate estimations can $ro"e e)treme!y sensiti"e to "a!ues of
com$ressibi!ity factor This is *hy the gas industry does not acce$t G%factor $redictions *ith a range of
uncertainty !arger than C 00< _ for custody transfer o$erations
Action Item
this modu!e
Please note:
date
Problem Set
< 6rite an essay that describes the a$$!icabi!ity of the -no*!edge gained in this course to se"era!
other areas in the $etro!eum and natura! gas business 'ro"ide s$ecific e)am$!es
Module Phase ,ia*rams- Part I
Module Goals
Module Goal: To fami!iari&e you *ith the basic conce$ts of $hase diagrams as a means of re$resenting
thermodynamic data
Module Objective: To high!ight the basic descri$tion of $hase diagrams of sing!e%com$onent systems
Introduction
One of the $rimary cha!!enges that *e face as engineers is ho* to communicate !arge quantities of com$!e)
information to our $eers and su$eriors 1or instance# *e may need to re$ort *hat thermodynamic changes
our *or-ing f!uid is undergoing 0ere# the fami!iar saying= 2 picture is worth a thousand words a$$!ies
A!though most non%engineers be!ie"e that the on!y !anguage an engineer s$ea-s is mathematics# in
actua!ity# the most effecti"e means that engineers use to communicate information in"o!"es the use of
$ictures or diagrams 'hase beha"ior is not an e)ce$tion (n $hase beha"ior thermodynamics# $hase
diagrams are used $recise!y for this $ur$ose
+!ase >iagra": A $hase diagram is a concise gra$hica! method of re$resenting $hase beha"ior of f!uids
(t $ro"ides an effecti"e too! for communicating a !arge amount of information about ho* f!uids beha"e at
different conditions
1irst of a!!# !et us c!assify f!uids into t*o broad grou$s on the basis of the number of com$onents that are
$resent in the system= $ure com$onent systems and mi)tures
T.o Classes o /luids
< 'ure%com$onent systems
2 Mi)tures
A!though this c!assification may seem tri"ia! at a first g!ance# it recogni&es the $aramount inf!uence of
composition on the $hase beha"ior of a f!uid system 6hereas for a sing!e%com$onent system# com$osition
is not a "ariab!e and therefore cannot inf!uence beha"ior# the beha"ior of a mi)ture is strong!y contro!!ed by
com$osition (n fact# as the number of com$onents in the system increases# the com$!e)ity of the $hase
diagram increases as *e!! Therefore# the sim$!est form of a $hase diagram is that of a system made of on!y
one com$onent (a $ure%com$onent system)
Pure!component Systems
5et us start *ith a *e!!%-no*n sing!e com$onent system= *ater . the most $!entifu! substance on earth
6hat is the beha"ior of *ater under different conditions of $ressure and tem$erature7 Or e"en more
s$ecific# is there a sing!e ans*er to the question= *hat is the boi!ing $oint of *ater7 Most $eo$!e *ou!d say#
@of course# <00 W3A# but a more accurate res$onse *ou!d $ose a c!arifying question= @At *hat $ressure7A (t is
common -no*!edge that *ater boi!s at <00 W3 (2<2 W1) at atmospheric pressure 8y requiring a $ressure
s$ecification in order to unique!y define the boi!ing $oint of *ater# *e are ac-no*!edging that the boi!ing
tem$erature of a $ure substance is pressure1dependent. (n rea!ity# *e are a!so im$!icit!y a$$!ying a "ery
usefu! thermodynamic $rinci$!e, the 3ibbs Rule# but this *i!! be the to$ic for !ater discussion
(n thermodynamics# *e refer to the Normal 4oiling Point as the boi!ing tem$erature of a f!uid at < atm of
$ressure (that is# atmospheric $ressure) Therefore# <00 W3 (2<2 W1) is the normal boi!ing $oint of water
6hat if *e *ant to communicate this idea7 6e *ou!d !i-e to communicate the conce$t that the tem$erature
at *hich *ater boi!s "aries *ith $ressure 6hat about a $icture to re$resent this information7 0ere is our first
phase diagram# 1igure 2< 6hereas se"era! sentences may be required to describe the "ariabi!ity of the
boi!ing $oint of *ater# the sing!e !ine sho*n in 1igure 2< is adequate 6hat does 1igure 2< te!! us7 (t te!!s
us that the boi!ing tem$erature of a !iquid increases as $ressure increases (n other *ords# it says that the
vapor pressure of a liquid increases as temperature increases That is to be e)$ected# because as the
tem$erature increases# more !iquid mo!ecu!es are ab!e to esca$e into the "a$or $hase# thus increasing the
$ressure that the aggregate of a!! "a$or mo!ecu!es e)ert on the system (ie "a$or $ressure)
Figure ).1: Eapor pressure curve 9or a pure substance
The cur"e in 1igure 2< is ca!!ed the vapor pressure curve or boiling point curve The !ine a!so re$resents the
dew point curve and the bubble point curve, one on to$ of the other This cur"e re$resents the transition
bet*een the "a$or and !iquid states
,einition o Basic Terms
Eapor +ressure: The $ressure that the "a$or $hase of a f!uid e)erts o"er its o*n !iquid at equi!ibrium at a
gi"en tem$erature
>e4 +oint: The $ressure and tem$erature condition at *hich an infinitesima! quantity of !iquid (a dro$!et)
e)ists in equi!ibrium *ith "a$or (t re$resents the condition of inci$ient !iquid formation in an initia!!y gaseous
system +otice that it can be a!so "isua!i&ed as a @!iquid systemA *here a!! but an infinitesima! quantity of
!iquid has been "a$ori&ed
Aubble +oint: The $ressure and tem$erature condition at *hich the system is a!! !iquid# and in equi!ibrium
*ith an infinitesima! quantity (a bubb!e) of gas This situation is# in essence# the o$$osite of that of the de*
$oint
7O$E: 1or single1component systems# one sing!e cur"e re$resents a!! three of these conditions ("a$or
$ressure# de* $oint and bubb!e $oint conditions) sim$!y because Eapor +ressure ' >e4 +oint '
Aubble +oint for unary systems
(n 1igure 2<# once a saturation $ressure has been se!ected# there is one (and on!y one) saturation
tem$erature associated *ith it This is on!y true for a sing!e com$onent system (n other *ords# this is the
only temperature )at the given pressure+, at which liquid and gas phase will co1e-ist in equilibrium. The ru!e
that go"erns the uniqueness of this $oint# for a sing!e%com$onent system# is ca!!ed the 3ibbs Phase Rule
This is the second time *e ha"e mentioned this ru!e# $ointing to its great im$ortance in $hase beha"ior 5et
us $ost$one any detai!ed discussion of the 4ibbs 'hase :u!e unti! !ater
Figure ).): Co"plete +8$ diagra" 9or pure8co"ponent s*ste"s
The "a$or cur"e# sho*n in 1igure 2<# re$resents the transition bet*een the "a$or and !iquid states for a
$ure com$onent Ob"ious!y# this is not the *ho!e story (f *e coo! the !iquid system# it ma-es sense to e)$ect
ice to form (a so!id $hase) 6e can communicate this ne* idea by adding more information to 1igure 2< (n
fact# there is a !ine that defines the !iquid%so!id transition, it is ca!!ed the solidification )or melting+ cur"e (see
1igure 22) 1urthermore# e"en though it is counter%intuiti"e# it is $ossib!e to go from so!id to "a$or *ithout
going through a !iquid state# if the $ressure is !o* enough This information can be added to the diagram by
inc!uding the sublimation curve Thus# 1igure 22 re$resents a more com$!ete $hase diagram for a $ure%
com$onent system
See ho* more and more information can be re$resented *ithin the !imits of the $hase diagram As
$etro!eum and natura! gas engineers# *e focus our attention on the 4oiling Point ,urve# as it re$resents the
transition bet*een !iquid and gas# the $hases *ith *hich *e dea! most often 5et us focus our attention on it
1igure 2D $resents a '%T diagram re$resenting the "a$or $ressure cur"e and its e)tremities T*o "ery
im$ortant thermodynamic $oints bound the "a$or $ressure cur"e= the ,ritical Point at its u$$er end and the
5riple Point at its !o*er end
Figure ).,: Eapor pressure curve and t!e triple and critical points
The 5riple Point is the meeting $oint of the "a$or $ressure# so!idification and sub!imation cur"es (see 1igure
22), hence# it re$resents the on!y condition at *hich a!! three $hases of a $ure substance (so!id# !iquid and
gas) can co%e)ist in equi!ibrium
At the ,ritical Point# gas and !iquid are in equi!ibrium *ithout any interface to differentiate them, they are no
!onger distinguishab!e in terms of their $ro$erties As *e reca!!# the on!y !ocation on the '%T diagram *here
!iquid and gas can be found together in equi!ibrium is along the vapor pressure curve 0ence# the critica!
$oint is c!ear!y the ma)imum "a!ue of tem$erature and $ressure at *hich !iquid and "a$or can be at
equi!ibrium This ma)imum tem$erature is ca!!ed the critical temperature )5c+, the corres$onding ma)imum
$ressure is ca!!ed the critical pressure )Pc+
5et us conc!ude this first modu!e by high!ighting the most im$ortant $ro$erties of the critica! $oint of $ure
substances# as sho*n be!o* The ne)t modu!e *i!! be $ro"iding more detai!s of interest that are embedded
in 1igure 2D
Properties O The Critical Point (Tc-Pc) (/or Pure Substances)0
< Tem$erature and $ressure for *hich !iquid and "a$or are no !onger distinguishab!e
2 1or T F Tc# !iquid and "a$or *i!! not co%e)ist# no matter *hat the $ressure is
D 1or ' F 'c# !iquid and "a$or *i!! not co%e)ist# no matter *hat the tem$erature is
Action Item
for this modu!e
Please note:
date
Problem Set
< S$ecu!ate on *hat the difference *ou!d be bet*een $hase diagrams ('%T cur"e) of "arious $ure
com$onent systems 6rite a $aragra$h or so on *hat you be!ie"e the differences are and *hy
2 6hat shou!d be the differences in the diagrams in question <7 Are the de* $oints the same7 6hat
about the bubb!e $oints7 And their critica! $oints7
Module Phase ,ia*rams- Part II
Module Goals
Module Goal: To fami!iari&e you *ith the basic conce$ts of $hase diagrams as a means of re$resenting
thermodynamic data
Module Objective: To fami!iari&e you *ith the use of '%T and '%" diagrams
8apor Pressure Curve
1rom the !ast modu!e you *i!! reca!! that the "a$or%$ressure cur"e (1igure 2D) and its e)tremities *ere
e)amined That figure is $resented in this modu!e in 1igure D< 6e conc!uded that t*o "ery im$ortant
thermodynamic $oints bound the "a$or $ressure cur"e= the ,ritical Point at its u$$er end and the 5riple
Point at its !o*er end
Figure ,.1: Eapor pressure curve
+o* !et us ta-e a second !oo- at this figure 6e can better understand the information re$resented by the
"a$or $ressure cur"e by !oo-ing at the $rocess of isobaric heating This is i!!ustrated by !ine A38 in 1igure
D2 The term @isobaricA $ertains to a constant pressure $rocess 8y isobaric heating $rocess# *e then mean
a @constant $ressure addition of heat into a systemA
Figure ,.): Eapor pressure curve and 6CA +at!
Such a $rocess can be described as fo!!o*s Starting at $oint A and mo"ing to*ards $oint 3 at constant
$ressure# *e add heat to the system 8y adding this heat# *e cause a tem$erature increase in the system
(Tem$erature at 3 F Tem$erature at A) At $oint 3# *hich !ies abo"e the "a$or $ressure or boi!ing $oint
cur"e# *e encounter a $hase change To the !eft of $oint 3# at !o*er tem$eratures# e)ists on!y !iquid To the
right of $oint 3# at higher tem$eratures# there is on!y "a$or Therefore# a sharp discontinuity in density e)ists
at $oint 3 Muring this transition# from !iquid to "a$or# *e *i!! notice that the heat that *e add to the system
does not cause any tem$erature increase# and in fact# tem$erature and $ressure conditions remain constant
during the transition re$resented by the "a$or cur"e (n other *ords# e"en though *e are adding heat# the
system remains at the $ressure and tem$erature associated *ith $oint 3 unti! the *ho!e $hase transition
has ta-en $!ace . ie# unti! a!! the "a$or is con"erted to !iquid (nstead of *or-ing to increase !iquid
tem$erature# this heat ser"es to mo"e !iquid mo!ecu!es a$art unti! a!! !iquid has become "a$or
Q$ to this $oint# *e sa* that the heat added before the system reached the $hase transition *as used to
raise the tem$erature of the substance 0o*e"er# the heat that *e are adding right no*# during the $hase
transition# is not causing any tem$erature increase (hence it is said to be hidden heat or !atent heat of
"a$ori&ation) Therefore# *e differentiate bet*een t*o -inds of heat= sensib!e heat and !atent heat
ensible @eat: (ts main $ur$ose is to cause an increase in tem$erature of the system
Datent @eat: (t ser"es on!y one $ur$ose= to con"ert the !iquid into "a$or (t does not cause a tem$erature
increase
(n fact# the name @!atentA suggests @hiddenA 0ere# *e are adding heat to the system but are not seeing its
effect in terms of tem$erature increase The heat that is needed to transform one mo!e of saturated !iquid
into "a$or is -no*n as the latent molar heat of vapori6ation=
Once *e ha"e con"erted a!! the !iquid into "a$or (ie# *e su$$!ied a!! the necessary !atent heat to
accom$!ish this)# *e may continue to add more heat (f *e do so# the tem$erature *i!! rise again and *e *i!!
end at $oint 8 (1igure D2) This heat is a!so sensible since it is causing the tem$erature of the system to
rise
(t is interesting to note that# in order to re"erse the $rocess from $oint 8 to $oint A# *e *i!! ha"e to remove
the e)act amount of heat that *e had added before This is a basic consequence of an energy ba!ance
$rinci$!e 6e ca!! such a re"erse $rocess an isobaric cooling process. 6e *i!! ha"e to remo"e some
sensible heat in order to coo! the "a$or from $oint 8 to 3# and then *e *i!! remo"e a!! the latent heat of the
"a$or to condense it into !iquid (transition at $oint 3) 1ina!!y# *e *i!! a!so need to remo"e more sensible
heat from the system for the coo!ing of the !iquid from $oint 3 to $oint A
(n the $re"ious t*o $rocesses# from A to 8 or "ice "ersa# *e had to cross the phase boundary re$resented
by the "a$or $ressure cur"e 0o*e"er# this is not the on!y thermodynamic $ath that is a"ai!ab!e for us to go
from A to 8 1igure DD de$icts another $ossib!e $ath
Figure ,.,: Eapor pressure curve and continuous pat! above critical point
(nstead of doing the *ho!e $rocess isobarically# *e may de"ise a ne* $ath that may a!so accom$!ish the
goa! of ta-ing the system from a condition VA/ to a condition V8/ 3onsider the $ath AME8 that is sho*n in
1igure DD
e:uence o9 +at!s
< 'ath AM= (sotherma! com$ression
2 'ath ME= (sobaric heating
D 'ath E8= (sotherma! e)$ansion
There is something remar-ab!e about this ne* $ath Qn!i-e the $re"ious $ath# notice that *e do not cross
the phase boundary at a!! The consequences of ta-ing this ne* road may seem astonishing at first g!ance=
*e *ent from an all1liquid condition ($oint A) to an all1vapor condition ($oint 8) without any sharp phase
transition (n fact# a!ong the $ath AME8 there is N7 $hase transition because *e ne"er crossed the $hase
boundary Since the $hase boundary re$resents a shar$ discontinuity in density (and other $hysica!
$ro$erties)# the fact that *e are not crossing it te!!s us that as *e go# there is actua!!y a gradation in density
(from a liquid li!e, or high%density at $oint A to a gas li!e, or !o*%density at $oint 8) instead of a shar$
change from the high !iquid density to the !o* gas density
6e *ere ab!e to do so because *e *ent abo"e the critica! conditions (n the "icinity of and beyond critica!
conditions# *e are no !onger ab!e to distinct!y !abe! the sing!e%$hase condition as either @!iquidA or @gasA
Qnder these conditions# any transition ta-es $!ace gradually *ithout any differentiation bet*een a V!iquid/ and
a Vgas/ $hase 6e ca!! this f!uid# *hich *e cannot define either as a !iquid or as a gas# a supercritical fluid (n
terms of density# a su$ercritica! f!uid may be described# at the same time# as a light !iquid (its density is not
as high as the !iquid density) and a heavy gas (its density is not as !o* as the ty$ica! gas density of the gi"en
substance) The beha"ior of f!uid around this area is an acti"e and interesting area of current research
(n summary# for a $ure substance# you can a"oid ha"ing an abru$t $hase transition (such as the one
described by the $ath A38) by going around the critica! $oint ($ath AME8) Hee$ in mind that any $ath that
crosses the "a$or $ressure cur"e (A38) *i!! undergo a $hase transition
P8 7ia$ram -or Pure Systems
(n the $re"ious discussion# *e used the '%T diagram and *ere not concerned about changes in the volume
of the system (f *e *ant to fo!!o* changes in "o!ume# *e may construct '%" or T%" diagrams# in *hich *e
ho!d tem$erature (T) or $ressure (') constant 5et us consider the case of a '%" Miagram (1igure DJ)
Figure ,.-: +8v >iagra" For 6 +ure Co"ponent
(n this case tem$erature is being he!d constant, our substance is undergoing an isothermal compression
process. Starting at E (a!!%"a$or condition)# an increase in $ressure *i!! resu!t in a rather significant reduction
in "o!ume since the gas $hase is com$ressib!e (f *e -ee$ com$ressing isotherma!!y# *e *i!! end u$ at $oint
1# *here the gas *i!! be saturated and the first dro$!et of !iquid *i!! a$$ear 6e ha"e come to the t*o%$hase
condition# *here !iquid (5) and "a$or (2) co%e)ist in equi!ibrium# for the first time# a!beit an infinitesima!
amount of !iquid
Once *e reach the t*o%$hase condition# *hat ha$$ens is not intuiti"e 6hi!e *e -ee$ on com$ressing by
decreasing the "o!ume ($ath 1%4#) the $ressure of the system remains constant, this condition continues
unti! all the "a$or has become !iquid 'oint 4 re$resents the !ast condition of !iquid and "a$or (5C2)
coe)istence# saturated !iquid condition (!iquid in equi!ibrium *ith an infinitesima! amount of "a$or) Once *e
ha"e on!y !iquid# if *e -ee$ on com$ressing (ie# attem$ting to reduce !iquid "o!ume) *e *i!! obser"e a ra$id
increase in $ressure# as indicated by the stee$ s!o$e in the '%" diagram This is because !iquid is "irtua!!y
incom$ressib!e# hence# a great dea! of $ressure is needed to cause a sma!! reduction in "o!ume
(t is im$ortant to recogni&e some $oints of this $rocess (f *e reca!! our $re"ious definitions of basic
conce$ts# *e *i!! recogni&e $oint 1# *here on!y a tiny quantity of !iquid e)ists in an other*ise com$!ete!y
gaseous system (the dew point of the system at the gi"en tem$erature) Simi!ar!y# 'oint 4 is the bubble
point, on!y an infinitesima!!y sma!! bubb!e of "a$or e)ists in an other*ise !iquid system
8ut *ait a second 5et us try to com$are 1igure DJ *ith 1igure D2 3an *e re!ate them to each other7
6here is $ath 1%4 in 1igure DJ re$resented in 1igure D2 (re$eated be!o*)7
Figure ,.) (repeated): Eapor pressure curve and 6CA +at!
The ans*er is# $ath 1%4 is re$resented by one $oint in 1igure D2, that is# $oint 3 :eca!!# for a sing!e%
com$onent system# de* $oints and bubb!e $oints are identica! Muring a $hase transition# both $ressure and
tem$erature must remain constant for $ure com$onents
+o*# if *e *ant to generate a!! the $ossib!e $oints that ma-e u$ the "a$or $ressure cur"e in 1igure D2# *e
*ou!d need to re$eat the e)$eriment for different tem$eratures 6e *ou!d end u$ *ith a fami!y of isotherms
(each simi!ar to the one $resented in 1igure DJ) This is re$resented in 1igure DO
Figure ,..: Fa"il* o9 +8v isot!er"s 9or a pure co"ponent
The &one *here the isotherms become f!at de!ineates the t*o%$hase region (t is c!ear!y seen that by $!otting
a!! the $airs in that &one ('<#T<)# ('2#T2)` ('c# Tc) *e *i!! be ab!e to re$roduce 1igure D2
(f *e no* dra* a !ine through a!! the 4ubble Points in 1igure DO# and then dra* a !ine connecting a!! the
.ew Points# *e *i!! end u$ *ith the 4ubble Point ,urve and the .ew Point ,urve, res$ecti"e!y (t is c!ear
that the t*o cur"es meet at the critica! $oint ('c# Tc) 1urthermore# the t*o cur"es de!ineate the $hase
en"e!o$e# *hich contains the 2%$hase region inside (f *e @c!eanA 1igure DO a !itt!e# *e end u$ *ith the
phase envelope that is sho*n in 1ig D6
Figure ,./: +8v >iagra" 6nd +!ase Envelope O9 6 +ure ubstance
(f you carefu!!y fo!!o* the trend of the critica! isotherm (R T B Tc in 1ig DO)# you *i!! rea!i&e that it has a $oint
of inf!e)ion (change of cur"ature) at the critica! $oint 1urthermore# the critica! $oint a!so re$resents the
ma)imum $oint (a$e)) of the '%" en"e!o$e Mathematica!!y# this information is con"eyed by the e)$ressions=
*hich are usua!!y -no*n as the criticality conditions These conditions are a!*ays satisfied at the critica!
$oint 6e *i!! comment more on this after *e begin the discussion on Equations of State (EOS) . semi%
em$irica! re!ationshi$s that mathematica!!y mode! the '%"%T beha"ior of f!uids
Action Item
for this modu!e
Please note:
date

Problem Set
< E)$!ain in your o*n *ords (no more than a $aragra$h) *hy the 2%'hase segment of the '%"
isotherm shou!d corres$ond to one sing!e $oint in the '%T diagram
2 6hat about the critica! $oint in the '%T diagram7 6hich '%" isotherm cou!d that corres$ond to7
D Ta-e t*o different hydrocarbons (say# 3< and 32) and com$are their '%T "a$or $ressure cur"es
6hat do you notice7 As you sa* in the $re"ious modu!e# those '%T cur"es *i!! be found at different
conditions of $ressure and tem$erature 8ut more than that# *hat can you comment about the
s!o$es of both cur"es7 Are they different7 6hy7 S$ecu!ate
Module Phase ,ia*rams- Part III
Module Goals
Module Goal: To fami!iari&e you *ith the basic conce$ts of 'hase Miagrams as a means of re$resenting
thermodynamic data
Module Objective: To introduce you to the additiona! com$!e)ity brought about by the $resence of one or
more additiona! com$onents
Binary Systems
Thus far# *e ha"e focused our attention on sing!e%com$onent systems (a!so ca!!ed unary# one%com$onent#
or $ure%com$onent systems) 0o*e"er# rea!%!ife systems are ne"er sing!e%com$onent, they are
mu!ticom$onent systems The sim$!est of this category is the binary system The good ne*s# ho*e"er# is
that the beha"ior of mu!ticom$onent systems are quite simi!ar to that of binary systems Therefore# *e *i!!
focus on binary systems# since they are easier to i!!ustrate
5et us $!ace t*o gases (A and 8) in an isotherma! ce!! As *e did before# *e *i!! -ee$ tem$erature constant
during this e)$eriment (sho*n in 1ig J<)
Figure -.1: Fsot!er"al EGperi"ent
(f *e mo"e the $iston do*n# *e *ou!d com$ress the gases# causing a decrease in "o!ume (n such a
scenario# an increase in $ressure *ou!d occur The $rocess starts at $oint 6# as sho*n in 1igure J2# an a!!%
"a$or condition
Figure -.): +8v >iagra" 9or a Ainar* MiGture
+othing here is ne* regarding the com$ression of the "a$or itse!f As $ressure increases# "o!ume decreases
according!y After some com$ression# the first dro$!et of !iquid *i!! a$$ear That is# *e ha"e found the dew
point of the mi)ture ($oint 8) 6e then $roceed *ith com$ression As *e further com$ress the system# more
!iquid *i!! a$$ear and the "o!ume *i!! continue to decrease
(t *ou!d a$$ear that *e are seeing here the same features as those of the sing!e%com$onent system that *e
studied in the $re"ious modu!es 8ut *ait a minute# is that so7
Actua!!y# there is a difference Muring the $hase transition# $ressure does not remain constant in this
e)$eriment (n fact# as com$ression $rogresses and more !iquid is formed# $ressure -ee$s rising . a!though
not as shar$!y as in the sing!e%$hase "a$or region 6hen the entire system has become !iquid# *ith on!y an
infinitesima! bubb!e of "a$or !eft# *e are at $oint 3 . the bubble point of the mi)ture '!ease note that# for
binary mi)tures (as is the case for mu!ticom$onent mi)tures#) the dew point and bubble point do not occur at
the same $ressure for isotherma! com$ression (f you reca!!# for the sing!e%com$onent system# the de* $oint
and the bubb!e $oint coincide This is not true for binary and mu!ticom$onent systems 3om$are 1igure J2
*ith 1igure DJ (re$eated be!o* from Modu!e D) to see this $oint
Figure -.) #repeated&: +8v >iagra" 9or a Ainar* MiGture
Figure ,.- #repeated&: +8v >iagra" For 6 +ure Co"ponent
<@H?? 6hy is $ressure increasing during the $hase transition7 At this $oint *e start to rea!i&e the *ays in
*hich composition $!ays a fundamenta! ro!e in the beha"ior of mi)tures
(n a sing!e%com$onent system# both !iquid and "a$or in the t*o%$hase region ha"e the same composition
(there is on!y one chemica! substance *ithin the system) +o*# *hen a mi-ture e)ists in a t*o%$hase
condition# different mo!ecu!es of different s$ecies are $resent and they can be either in a !iquid or "a$or
state (t*o%$hase condition) Some of them *ou!d @$referA to be in the gas $hase *hi!e the others *ou!d
@$referA to be in the !iquid $hase This @$referenceA is contro!!ed by the volatility of the gi"en com$onent
6hen *e reach $oint 8 (1igure J2) and the first dro$!et of !iquid a$$ears# the heaviest mo!ecu!es are the
ones that $referentia!!y go to that first tiny dro$!et of !iquid $hase 1or Vhea"y/ mo!ecu!es# gi"en the choice# it
is more desirable to be in the condensed state
As *e -ee$ on forming more !iquid (by com$ression)# main!y !ight mo!ecu!es remain in the "a$or $hase
0o*e"er# at the end $oint of the transition ($oint 3 in 1igure J2) *e ha"e forced a!! of them to go to the
!iquid state . they no !onger ha"e a choice This enforcement requires greater $ressure (f you com$are a
sam$!e of !iquid at de* $oint conditions ($oint 8 in 1igure J2) to one ta-en in the midd!e of the transition# it
is c!ear that the former *ou!d be richer in hea"y com$onents than the !atter The $ro$erties of the hea"iest
com$onent *ou!d be most inf!uentia! at the de* $oint (*hen the !iquid first a$$ears), *hi!e the $ro$erties of
the !ighter com$onent *ou!d be most inf!uentia! at the bubb!e $oint (*hen the !ast bubb!e is about to
disa$$ear)
(n the t*o%$hase region# $ressure increases as the system $asses from the de* $oint to the bubb!e $oint
The com$osition of !iquid and "a$or is changing, but . *atch out^ . the o"era!! com$osition is a!*ays the
same^ At the dew point# the com$osition of the "a$or is equa! to the o"era!! com$osition of the system,
ho*e"er# the infinitesima! amount of !iquid that is condensed is richer in the !ess "o!ati!e com$onent At the
bubble point# the com$osition of the !iquid is equa! to that of the system# but the infinitesima! amount of
"a$or remaining at the bubb!e $oint is richer in the more "o!ati!e com$onent than the system as a *ho!e
(n genera!# *hen t*o different s$ecies are mi)ed# some of the beha"iors of the indi"idua! s$ecies and their
$ro$erties *i!! change Their usual beha"ior (as $ure com$onents) *i!! be a!tered as a consequence of the
ne* fie!d of mo!ecu!ar interactions that has been created 6hi!e -e$t in a $ure condition# mo!ecu!es on!y
interact *ith !i-e mo!ecu!es On the other hand# in a mi)ture ne* interactions bet*een dissimi!ar mo!ecu!es
occur
Our ne)t ste$# in order to continue this discussion in a coherent manner# is to dra* the com$!ete '%2
diagram for this binary mi)ture by de!ineating the t*o%$hase region (n the same *ay as *e did $re"ious!y#
*e de!ineate the t*o%$hase region by dra*ing a com$!ete fami!y of isotherms in the '%2 diagram 1igure JD
i!!ustrates this
Figure -.,: Fa"il* o9 Fsot!er"s on a +8E diagra" Ainar* MiGture
Again# the !ine connecting a!! of the bubb!e and de* $oints *i!! generate the bubble and dew point curve#
both of *hich meet at the critica! $oint +otice that the critica! $oint does not re$resent a ma)imum in the '%
2 diagram of a mi)ture A!so note that bubb!e $oint $ressures and de* $oint $ressures are no !onger the
same
Again# the isotherms through the t*o%$hase region are not hori&onta! but ha"e a definite s!o$e This must
ha"e an im$!ication (n fact# it does 6hat if *e no* *ant to $!ot the '%T diagram for this mi)ture7 6i!! *e
ha"e on!y a single !ine# *here bubb!e and de* $oint cur"es !ie on to$ of each other# as *e had for a sing!e%
com$onent system7 Of course not (nstead of both cur"es being together# the bubb!e $oint cur"e *i!! shift to
the u$$er !eft (higher $ressures) and de* $oint cur"e *i!! shift to the !o*er right (!o*er $ressures) . both of
them meeting at the critica! $oint 1igure JJ sho*s us a ty$ica! $hase en"e!o$e for a mi)ture
Figure -.-: +8$ +!ase Envelope For 6 Ainar* *ste"
+otice the enormous difference bet*een the '%T cur"e of a mu!ti%com$onent system (binary system in this
case# 1ig JJ) and the '%T cur"e of a $ure (sing!e) com$onent (1ig D< of Modu!e D# re$eated be!o*) The
on!y system for *hich the bubb!e $oint cur"e *i!! coincide *ith the de* $oint cur"e is a sing!e com$onent
system# *here *e ha"e a sing!e !ine for the '%T diagram (for e)am$!e# the boi!ing $oint cur"e re$resented in
1ig D<) (n 1ig D<# the critica! $oint re$resents the ma)imum set of ('#T) "a!ues that you cou!d find in the '%
T gra$h
Figure ,.1 (repeated) I Eapor pressure curve
This is not a!! There are some other im$!ications 3an *e say no* that the critica! $oint is the ma)imum
"a!ue of $ressure and tem$erature *here !iquid and gas can coe)ist7 5oo- at 1igure JJ again Ob"ious!y
not The critica! $oint is no !onger at the a$e) or $ea- of the t*o%$hase region, hence# "a$or and !iquid can
coe)ist in equi!ibrium at T F Tc and ' F 'c (n fact# *e can identify t*o ne* ma)ima= condition 'cc is the
ma)imum $ressure and condition Tcc is the ma)imum tem$erature at *hich 5C2 *i!! be found in equi!ibrium
6e assign s$ecia! names to these $oints There are the cricondenbar and cricondentherm, res$ecti"e!y
3!ear!y# the on!y definition that no* can sti!! ho!d for the critica! $oint . both for mi)tures and $ure
com$onents . is the one sho*n be!o*
Critical +oint #+c;$c&: The tem$erature and $ressure for *hich !iquid and "a$or are indistinguishab!e
Again# this definition is a$$!icab!e both for mi)tures and $ure%com$onent systems, it does not ma-e any
reference to ma)imum "a!ues in the cur"e These ma)imum "a!ues# as *e said# ha"e s$ecia! names in the
case of mi)tures Thus# for mi)tures# *e ha"e to additiona!!y define=
Cricondent!er" #$cc&:
< The highest tem$erature in the t*o%$hase en"e!o$e
2 1or T F Tcc# !iquid and "a$or cannot co%e)ist at equi!ibrium# no matter *hat the $ressure is

Cricondenbar #+cc&:
< The highest $ressure in the t*o%$hase en"e!o$e
2 1or ' F 'cc# !iquid and "a$or cannot co%e)ist at equi!ibrium# no matter *hat the tem$erature is
(n the case of the unary system# besides de* and bubb!e $oint cur"es !ying on to$ of each other# it is c!ear
that cricondentherm# cricondenbar# and critica! conditions are a!so re$resented by a sing!e $oint (that is# the
critica! $oint itse!f) This is c!ear from a!! three $re"ious definitions Thus# as *e sa* before# the definition for
critical point in unary systems encom$asses a!! three of the definitions gi"en abo"e
For pure substances onl*:
3ricondentherm B 3ricondenbar B 3ritica! 'oint
Retro$rade Phenomenon
:egarding mu!ti%com$onent mi)tures (*here the binary system is the sim$!est case)# some interesting
$henomenon $rofound!y differentiate their beha"ior from the beha"ior of sing!e%com$onent systems 6e are
no* ta!-ing about retrograde phenomena
(n the $re"ious section# *e !earned ho* the @critical pointA for a sing!e%com$onent system meant e"erything=
the highest $ressure and tem$erature at *hich t*o $hases can e)ist and the $oint for *hich !iquid and "a$or
$hases are indistinguishab!e Then *e !earned that this is not the case for mu!ticom$onent systems
A!though the critica! $oint for these systems is the common $oint bet*een the de* and bubb!e $oint cur"es
(the $oint for *hich !iquid and "a$or $hases are indistinguishab!e)# in genera!# this $oint neither re$resents
the ma)imum $ressure nor the ma)imum tem$erature for "a$or%!iquid coe)istence (n fact# *e ga"e ne*
names to these ma)ima= cricondenbar (for the ma)imum $ressure) and cricondentherm (for the ma)imum
tem$erature) 5et/s !oo- at this again in 1igure JO# *here the critica! $oint ('c# Tc)# cricondentherm (Tcc)# and
cricondenbar ('cc) are high!ighted
Figure -..: Cricondenbar; Cricondent!er" and Critical +oint
'!ease reca!! that the bubble point curve re$resents the !ine of saturated !iquid (<00 _ !iquid *ith an
infinitesima! amount of "a$or) and the dew point curve re$resents the !ine of saturated "a$or (<00 _ "a$or
*ith an infinitesima! amount of !iquid) These conditions are a!! sho*n in 1igure JO
5et us no* consider the isotherma! $rocesses ta-ing $!ace at T B T< and T B T2# re$resented in 1igure J6
Figure -./: Fsot!er"al Co"pression 6t $1 and $)
1igure J6 sho*s us t*o cases of isotherma! com$ression for t*o different tem$eratures T< and T2 +otice
that these tem$eratures are such that $1 ( $c and $c ( $) ( $cc.
(t is common -no*!edge that an isotherma! com$ression (increasing $ressure *hi!e tem$erature is he!d
constant) causes the condensation of a "a$or (steam# in the case of *ater) That is the normal or e-pected
behavior of a "a$or under com$ression= the more you com$ress it# the more !iquid you get out of it after the
saturation conditions ha"e been reached This is a!*ays true for a pure1component system# such as *ater
6e!!# that is e-actly *hat is ha$$ening for our first case# the isotherma! com$ression at T B T< At $oint A# *e
are in an A55 2A'O: condition (0 _ !iquid) and *e are starting to cross o"er into the t*o%$hase region As
*e com$ress from $oint A to 8# more and more !iquid is formed unti! the entire system has been condensed
($oint 8) 6e *ent a!! the *ay from 0 _ !iquid to <00 _ !iquid# as *e e)$ected# by com$ressing the "a$or
0o* !iquid yie!d $rogresses *ith $ressure is sho*n in 1igure JK
Figure -.0: Di:uid Hield For $!e Fsot!er"al Co"pression 6t $1
Again# there is nothing contrary to e)$ectations here# and *e *ou!d get the same resu!t as !ong as $ ( $c.
0o*e"er# there is something "ery interesting going on *ithin the region $c ( $ ( $cc.
(n the second case ($c ( $) ( $cc)# *e ha"e a different beha"ior At $oint 3 (1igure J6)# *e are starting in an
A55 2A'O: condition (0 _ !iquid), by increasing $ressure# *e force the system to enter the t*o%$hase
region Thus# some !iquid has to dro$ out, *e e)$ect that as the $ressure -ee$s increasing# *e *i!! $roduce
more and more !iquid That is true to some e)tent` 8QT# !oo- at the fina! $oint of our 9ourney# $oint M=
a!though *e are $roducing !iquid# our fina! condition (de* $oint) requires us to ha"e 0 _ !iquid in the system
again
@o4 so?? This is te!!ing us that# as *e are entering the t*o%$hase region# *e *i!! start to $roduce some
!iquid, but# there *i!! be a $oint (of ma)imum !iquid yie!d) *here that !iquid *i!! start to "a$ori&e ($oint 3/) (n
other *ords# e"en though *e are com$ressing the system# !iquid *i!! vapori6e and not condense (sn/t this
contrary to e)$ectations7 ;es# and that is *hy *e ca!! this a retrograde (contrary to e)$ectation) behavior.
1igure J8 sho*s a ty$ica! cur"e for the "ariation of the !iquid "o!ume $ercentage *ith $ressure This cur"e
can be a!so referred to as the liquid dropout curve
Figure -.1: Di:uid Hield For $!e Fsot!er"al Co"pression 6t $)
The increase in the !iquid fraction *ith decreasing $ressure bet*een $oints 3 and M is e)act!y the o$$osite
of the norma! trend This beha"ior# ho*e"er# is ty$ica! of gas condensate systems :etrograde conditions
may be encountered in dee$%*e!! gas $roduction# as *e!! as in reser"oir conditions
1or $roduction o$erations# usua!!y the ob9ecti"e is to maintain $ressure so as to achie"e ma)imum !iquid
dro$out The initia! '2T conditions of the *e!! may corres$ond to a $oint abo"e $oint M (f the conditions at
the *e!!head are then maintained near $oint 3/# !iquid reco"ery is ma)imi&ed at the surface 0o*e"er#
ma)imum !iquid dro$out is not a!*ays sought At reser"oir conditions# $resence of !iquid is not desirab!e in a
gas reser"oir# because !iquids ha"e neg!igib!e mobi!ity (at !o* saturations) and thus# the hydrocarbon *ou!d
be . for $ractica! $ur$oses . !ost fore"er 5iquid a!so im$airs gas mobi!ity, hence# !iquid $roduction at
reser"oir conditions is to be a"oided at a!! times in a gas reser"oir This is often achie"ed by re$ressuri&ation
or !ean gas in9ection
(t is a!so im$ortant to see that a simi!ar beha"ior is to be e)$ected *ithin the region +c ( + ( +cc. (n this case#
*e ta!- about retrograde vapori6ation since *e *i!! be mo"ing from a <00 _ !iquid to another <00 _ !iquid
condition (both on the bubb!e $oint cur"e) in an isobaric heating
Action Item
for this modu!e
Please note:
date
Problem Set
< 3om$are and contrast the definition of critica! $oint for a sing!e com$onent system and a mi)ture
6hat is common bet*een these t*o systems and *hat is not7 E)$!ain
2 Mo the cricondentherm and cricondenbar $!ay a simi!ar ro!e as the critica! $oint7 (f not# *hy7 6hat
is the difference7
D (n a cou$!e of sentences# s$ecu!ate on the $hysics of *hy *e ha"e retrograde $henomena
J 3om$are and contrast the 2%'hase segment of the '%" isotherm for sing!e com$onents and the '%"
isotherm for a binary system 6hat is the difference7
Module Phase ,ia*rams- Part I!
Module Goals
Module Goal: To fami!iari&e you *ith the basic conce$ts of 'hase Miagrams as a means of re$resenting
thermodynamic data
Module Objective: To fami!iari&e you *ith the $rocess of e)tracting quantitati"e com$ositiona! information
from $hase en"e!o$es
E--ect o- Composition on Phase Behavior
5et us try to reconci!e the '%T gra$hs for the binary mi)ture *ith *hat *e -no* from '%T gra$hs for sing!e%
com$onent systems At the end of the day# a mi)ture is formed by indi"idua! com$onents *hich# *hen $ure#
act as $resented in the '%T diagram sho*n in 1ig D< XModu!e D# re$eated be!o*Y 6e *ou!d# therefore#
e)$ect that the '%T diagram of each $ure com$onent *i!! ha"e some sort of inf!uence on the '%T diagram of
any mi)ture in *hich it is found
Figure ,.1 (repeated): Eapor pressure curve
(n fact# it *ou!d be reasonab!e to thin- that as the $resence of a gi"en com$onent A dominates o"er 8# the
'%T gra$h of that mi)ture (AC8) shou!d get c!oser and c!oser to that of A as a $ure com$onent
6hat this is te!!ing us is that a ne* "ariab!e is coming into the $icture= composition. So far *e ha"e not
considered the ratio of com$onent A to com$onent 8 in the system +o* *e are going to study ho* different
ratios (com$ositions) *i!! gi"e different en"e!o$es# ie# different '%T beha"iors
5et us say that *e ha"e a mi)ture of com$onents A (Methane# 30J) and 8 (Ethane# 3206)# *here A is the
more "o!ati!e of the t*o (t is c!ear that for the t*o $ure com$onents# *e *ou!d ha"e two boi!ing $oint cur"es
for each com$onent (A and 8) as sho*n in 1igure O<
Figure ..1: +8$ Grap!s For $!e +ure Co"ponents 6 6nd A
(Bloomer, O.T., Gami, D.C., Parent, J.D., PhysicalChemical Properties o! "ethane#thane
"i$tures%. Copyri&ht '()*, +nstitute o! Gas Technolo&y (no, Gas Technolo&y +nstitute%, in
Chica&o). -esearch Bulletin .o. '/.)
'!ease notice that the $osition of each of cur"e *ith res$ect to the other de$ends on its "o!ati!ity Since *e
are considering A to be the more "o!ati!e# it is e)$ected to ha"e higher "a$or $ressures at !o*er
tem$eratures# thus# its cur"e is !ocated to*ards the !eft 1or 8# the !ess "o!ati!e com$onent# *e ha"e a
boi!ing $oint cur"e *ith !o*er "a$or $ressures at higher tem$eratures 0ence# the boi!ing $oint cur"e of 8 is
found to*ards the right at !o*er $ressures
+o*# if *e mi) A and 8# the ne* $hase en"e!o$e can be anywhere *ithin cur"es A and 8 This is sho*n in
1igure O2# *here the effect of com$osition on $hase beha"ior of the binary mi)ture Methane>Ethane is
i!!ustrated
Figure ..): E99ect O9 Co"position On +!ase Ae!avior.
(Bloomer, O.T., Gami, D.C., Parent, J.D., PhysicalChemical Properties o! "ethane#thane
"i$tures%. Copyri&ht '()*, +nstitute o! Gas Technolo&y (no, Gas Technolo&y +nstitute%, in
Chica&o). -esearch Bulletin .o. '/.)
(n 1igure O2# each $hase en"e!o$e re$resents a different com$osition or a $articu!ar com$osition bet*een A
and 8 ($ure conditions) The $hase en"e!o$es are bounded by the $ure%com$onent "a$or $ressure cur"e
for com$onent A (Methane) on the !eft# that for com$onent 8 (Ethane) on the right# and the critica! !ocus (ie#
the cur"e connecting the critica! $oints for the indi"idua! $hase en"e!o$es) on the to$ +ote that *hen one of
the com$onents is dominant# the cur"es are characteristic of re!ati"e!y narrow1boiling systems# *hereas the
cur"es for *hich the com$onents are $resent in com$arab!e amounts constitute re!ati"e!y wide1boiling
systems
+otice that the range of tem$erature of the critica! $oint !ocus is bounded by the critica! tem$erature of the
$ure com$onents for binary mi)tures Therefore# no binary mi)ture has a critica! tem$erature either be!o*
the !ightest com$onent/s critica! tem$erature or abo"e the hea"iest com$onent/s critica! tem$erature
0o*e"er# this is true on!y for critica! tem$eratures, but not for critica! $ressures A mi)ture/s critica! $ressure
can be found to be higher than the critica! $ressures of both $ure com$onents . hence# *e see a conca"e
sha$e for the critica! !ocus (n genera!# the more dissimi!ar the t*o substances# the farther the u$*ard reach
of the critica! !ocus 6hen the substances ma-ing u$ the mi)ture are simi!ar in mo!ecu!ar com$!e)ity# the
sha$e of the critica! !ocus f!attens do*n
P!5 and 4!5 7ia$rams
(n addition to considering "ariations *ith $ressure# tem$erature# and "o!ume# as *e ha"e done so far# it is
a!so "ery constructi"e to consider "ariations *ith com$osition Most !iterature on the sub9ect ca!!s these
diagrams the @'%)A and @T%)A diagrams res$ecti"e!y 0o*e"er# a *ord of caution is needed in order not to
confuse the reader E"en though @)A stands for @com$ositionA . in a genera! sense . here# *e *i!! see in
the ne)t section that it is a!so customary to use @)A to sing!e out the com$osition of the liquid $hase (n fact#
*hen *e are dea!ing *ith a mi)ture of !iquid and "a$or# it is customary to refer to the com$osition of the
!iquid $hase as @)iA and use @yiA for the com$osition of the "a$or $hase @)iA $ertains to the amount of
com$onent in the !iquid $hase $er mo!e of !iquid $hase# and @yiA $ertains to the amount of com$onent in the
"a$or $hase $er mo!e of "a$or $hase 0o*e"er# *hen *e ta!- about com$osition in genera!# *e are rea!!y
ta!-ing about the overall com$osition of the mi)ture# the one that identifies the amount of com$onent $er unit
mo!e of mi-ture (t is more con"enient to ca!! this o"era!! com$osition @&iA (f *e do so# these series of
diagram shou!d be ca!!ed @'%&A and @T%&A diagrams This is a !itt!e a*-*ard in terms of traditiona! usage, and
hence# *e ca!! them @'%)A and @T%)A *here @)A here refers to o"era!! com$osition as o$$osed to !iquid
com$osition
A '%) diagram for a binary system at constant tem$erature and a T%) diagram for a binary system at a
constant $ressure are dis$!ayed in 1igures OD and OJ# res$ecti"e!y The !ines sho*n on the figures
re$resent the bubb!e and de* $oint cur"es +ote that the end $oints re$resent the $ure%com$onent boi!ing
$oints for substances A and 8
Figure ..,: +8J >iagra" For Ainar* *ste"
Figure ..-: $8J >iagra" For Ainar* *ste"
(Courtesy o! 01O"+C, +.C)
(n a '%) diagram (1igure OD)# the bubb!e $oint and de* $oint cur"es bound the t*o%$hase region at its to$
and its bottom# res$ecti"e!y The sing!e%$hase !iquid region is found at high $ressures, the sing!e%$hase
"a$or region is found at !o* $ressures (n the T%) diagram (1igure OJ)# this ha$$ens in the re"erse order,
"a$or is found at high tem$eratures and !iquid at !o* tem$eratures 3onsequent!y# the bubb!e $oint and de*
$oint cur"e are found at the bottom and the to$ of the t*o%$hase region# res$ecti"e!y
4he @ever Rule
'%) and T%) diagrams are quite usefu!# in that information about the com$ositions and re!ati"e amounts of
the t*o $hases can be easi!y e)tracted (n fact# besides gi"ing a qua!itati"e $icture of the $hase beha"ior of
f!uid mi)tures# $hase diagrams can a!so gi"e quantitati"e information $ertaining to the amounts of each
$hase $resent# as *e!! as the com$osition of each $hase
1or the case of a binary mi)ture# this -ind of information can be e)tracted from '%) or T%) diagrams
0o*e"er# the difficu!ty of e)tracting such information increases *ith the number of com$onents in the
system
At a gi"en tem$erature or $ressure in a T%) or '%) diagram (res$ecti"e!y)# a hori&onta! !ine may be dra*n
through the t*o%$hase region that *i!! connect the com$osition of the !iquid ()A) and "a$or (yA) in equi!ibrium
at such condition . that is# the bubb!e and de* $oints at the gi"en tem$erature or $ressure# res$ecti"e!y (f#
at the gi"en $ressure and tem$erature# the o"era!! com$osition of the system (&A) is found *ithin these
"a!ues ()A E &A E yA in the T%) diagram or yA E &A E )A in the '%) diagram)# the system *i!! be in a t*o%$hase
condition and the "a$or fraction (a4) and !iquid fraction (a5) can be determined by the !e"er ru!e=
#..1a& #..1b&
+ote that a5 and a4 are not inde$endent of each other# since a5 C a4 B < 1igure OO i!!ustrates ho* equations
(O<) can be rea!i&ed gra$hica!!y This figure a!so he!$s us understand *hy these equations are ca!!ed @the
!e"er ru!eA Sometimes it is a!so -no*n as the @re"erse arm ru!e#A because for the ca!cu!ation of a5 (!iquid)
you use the @armA *ithin the (yA%)A) segment c!osest to the vapor# and for the "a$or ca!cu!ation (a4) you use
the @armA c!osest to the liquid.
Figure ...: $!e Dever Rule Fn a +8G >iagra"
At this $oint you *i!! see c!ear!y *hy *e needed to ma-e a c!ear distinction among @)iA and @yiA and @&iA
E)$ressions (O<) can be deri"ed from a sim$!e materia! ba!ance 3an you $ro"e it7 XHint: The number of
mo!es of a com$onent @iA $er mo!e of mi)ture in the !iquid $hase is gi"en by the $roduct @)ia5A# *hi!e the
number of mo!es of @iA $er mo!e of mi)ture in the gas is gi"en by @yia4A Since there are @&iA mo!es of
com$onent @iA $er mo!e of mi)ture# the fo!!o*ing must ho!d= 3an you $roceed from
here7Y
4ernary Systems
The ne)t more com$!e) ty$e of mu!ti%com$onent system is a ternary# or three%com$onent# system Ternary
systems are more frequent!y encountered in $ractice than binary systems 1or e)am$!e# air is often
a$$ro)imated as being com$osed of nitrogen# o)ygen# and argon# *hi!e dry natura! gas can be rather
crude!y a$$ro)imated as being com$osed of methane# nitrogen and carbon dio)ide 6e can a!so ha"e
$seudo D%com$onent systems# *hich consist of mu!ticom$onent systems (more than D com$onents) that
can be described by !um$ing a!! com$onents into D grou$s# or $seudo%com$onents (n this case# each grou$
is treated as a sing!e com$onent 1or e)am$!e# in 3O2 in9ection into an oi! reser"oir# 3O2# 3<# and 32 are
often !um$ed into a sing!e !ight $seudo%com$onent# *hi!e 3D to 36 form the intermediate $seudo%com$onent#
and the others (38C) are !um$ed together into a sing!e hea"y $seudo%com$onent
(ntuiti"e!y# ha"ing more than t*o com$onents $oses a $rob!em *hen a $ictoria! re$resentation is desired A
rectangu!ar coordinate $!ot# ha"ing on!y t*o a)es# *i!! no !onger suffice 4ibbs first $ro$osed the use of a
triangular coordinate system (n modern times# *e use an equi!atera! triang!e for such a re$resentation
1igure O6 sho*s an e)am$!e of a ternary $hase diagram +ote that the re!ationshi$ among the
concentrations of the com$onents is more com$!e) than that of binary systems
Figure ../: $!ree8Co"ponent $riangular Representation
1eatures=
Any $oint *ithin this triang!e re$resents the o"era!! com$osition of a ternary system at a fi)ed
tem$erature and $ressure
8y con"ention# the !ightest com$onent (5) is !ocated at the a$e) or to$ of the triang!e The hea"y
(0) and medium (M) com$onents are $!aced at the !eft hand corner and right hand corner#
res$ecti"e!y
E"ery corner re$resents a $ure condition 0ence# at the to$ *e ha"e <00 _ 5# and at each side#
<00 _ 0 and <00 _ M# res$ecti"e!y
Each side of the triang!e re$resents a!! $ossib!e binary combinations of the three com$onents
On any of those sides# the fraction of the third com$onent is &ero (0_)
As you mo"e from one side (0 _) to the <00 _ or $ure condition# the com$osition of the gi"en
com$onent is increasing gradua!!y and $ro$ortiona!!y At the "ery center of the triang!e# *e find
DDDD _ of each of the com$onent
To differentiate *ithin the t*o%$hase region and sing!e%$hase region in the ternary diagram# $ressure and
tem$erature must be fi)ed There *i!! be different en"e!o$es (binoda! cur"es) at different $ressures and
tem$eratures The binoda! cur"e is the boundary bet*een the 2%$hase condition and the sing!e%$hase
condition (nside the binoda! cur"e or $hase en"e!o$e# the t*o%$hase condition $re"ai!s (f *e fo!!o* the
con"ention gi"en abo"e (!ights at the to$# hea"ies and mediums at the sides)# the t*o%$hase region *i!! be
found at the to$ This can be seen more c!ear!y in 1igure OK
Figure ..0: $ernar* +!ase >iagra" For 6 $ernar* *ste"
(Courtesy o! 01O"+C, +.C)
The binoda! cur"e is formed of the bubble point curve and the dew point curve, both of *hich meet at the
plait point This is the $oint at *hich the !iquid and "a$or com$osition are identica! (resemb!es the critical
point that *e studied before) 6ithin the t*o%$hase region# the tie lines are straight !ines that connect the
com$ositions of the "a$or and !iquid $hase in equi!ibrium (bubb!e $oint to the de* $oint) These tie !ines
ang!e to*ards the medium%com$onent corner (t can a!so be recogni&ed that any mi)ture on a tie !ine has
the same !iquid and "a$or com$ositions
1ina!!y# to find the $ro$ortion of !iquid and "a$or at any $oint on the tie !ine# *e a$$!y the lever rule
Multicomponent Mi5tures
1or systems containing more than three com$onents# $ictoria! re$resentation becomes difficu!t# if not
im$ossib!e Sim$!e diagrams can be obtained if the mo!e fractions of a!! but t*o or three com$onents remain
constant# and the "ariation of the t*o or three "arying com$onents *ith tem$erature and $ressure are
sho*n
(n $ractica! a$$!ications# the mo!e fractions of a!! com$onents can be e)$ected to "ary 1or such systems#
direct ca!cu!ations based on $hysica! mode!s are the on!y *ay to obtain re!iab!e information about the
system $hase beha"ior This is the u!timate goa! of this series of modu!es# and these ca!cu!ations *i!! be
studied in detai! as the course $rogresses
Action Item
for this modu!e
Please note:
date
Problem Set
< 1igure O2 sho*s the '%T $hase en"e!o$es for eight binary mi)tures of Methane and Ethane at
eight different com$ositions The data *as e)$erimenta!!y generated at (4T ((nstitute of 4as
Techno!ogy) and $resented in the :esearch 8u!!etin +o 22 The "a$or $ressure cur"es of Methane
and Ethane bound the $hase en"e!o$es of the eight binary mi)tures of Methane and Ethane at
different $ro$ortions 1rom !eft to right# these $ro$ortions (mo!ar com$ositions) are=
Mi)ture < IKO0_ 30J and 2O0_ 3206 (c!osest to <00_ $ure Methane "a$or $ressure cur"e)
Mi)ture 2 I2O0_ 30J and KO0_ 3206
Mi)ture D 8O<6_ 30J and <J8J_ 3206
Mi)ture J K000_ 30J and D000_ 3206
Mi)ture O O002_ 30J and JII8_ 3206
Mi)ture 6 D002_ 30J and 6II8_ 3206
Mi)ture K <JI8_ 30J and 8O02_ 3206
Mi)ture 8 O00_ 30J and IO00_ 3206 (c!osest to <00_ $ure Ethane "a$or $ressure cur"e)
2 Qsing this $hase beha"ior data# generate the '%) and T%) diagram for Methane>Ethane mi)tures at
T B S J0 1 and ' B O00 $sia res$ecti"e!y
D (f a certain amount of the mi)ture J0_ 3< S 60_ 32 is -e$t in a "esse! at O00 $sia# determine the
tem$erature at *hich the "esse! has to be sub9ected if at !east O0_ of the substance is required to
be in the !iquid state 0o* *ou!d your ans*er change if *e *ere no* required to ha"e <0_ of
!iquid in the "esse!7 0o* *ou!d it change if the o"era!! com$osition is no* considered to be 60_ 3<
and J0_ 32 7
J <0 !bmo! of an equimo!ar 3<>32 mi)ture is confined inside a "esse! at conditions of S 60
o
1 and O00
$sia 6hat is the $ercentage of !iquid inside the "esse!7 6hat is the com$osition of the !iquid and
"a$or at such condition7
O 6hat *ou!d be the com$osition of the first bubb!e that a$$ears in a isotherma! e)$ansion of a !iquid
at S J0
o
17 At *hich $ressure *ou!d this bubb!e a$$ear7 6hat *ou!d be the $ressure at *hich the
first dro$!et a$$ears in a isotherma! com$ression of a "a$or at S J0
o
17 6hat is the com$osition of
such a dro$!et7
6 3an you a$$!y the !e"er ru!e to in a ternary diagram7 (f not# *hy not7 6hat about a mu!ticom$onent
system7
Module PT Behavior and E1uations o State (EOS)-
Part I
Module Goals
Module Goal: To introduce you to quantification in f!uid $hase beha"ior
Module Objective: To quantitati"e!y and qua!itati"e!y com$are idea! and rea! gas beha"ior
Part I
Introduction
The u!timate $ur$ose of this course is to bui!d a firm -no*!edge of the $hase beha"ior of f!uids 6ith this
understanding# *e *i!! be ab!e to estab!ish the basis and rationa!e u$on *hich $hase beha"ior a$$!ications
in $roduction systems are grounded 6e are using the *ord production in a generic sense# that is# *here it
$ertains to reser"oir# $i$e!ine# and the surface $roduction (of any $roduced f!uid)
So far# *e ha"e seen that much of the im$ortance that *e $!ace on understanding $hase beha"ior comes
from the abi!ity that it gi"es us to $redict ho* a gi"en system *i!! beha"e at different conditions 6e need
$hase diagrams to !oo- at *hat the state of the system that *e are dea!ing *ith is, that is# *hat is its origina!
state As a matter of fact# if *e !oo- at $etro!eum $roduction# *e often ta!- about a thermodynamic $rocess
that is ta-ing $!ace# in"o!"ing a $rocess $ath simi!ar to one that *e ha"e seen in any basic thermodynamics
course
Lust to gi"e an i!!ustration# consider 1igure 6<
Figure /.1. Fsot!er"al >epletion O9 6 @*drocarbon Reservoir
'roduction# as defined abo"e# in"o!"es ta-ing the reser"oir from an initia! condition ('A # Tf) to fina! state of
de$!etion ('8 # Tf)# ('M # Tf)# ('E # Tf) or e"en ('1 # Tf) Once the end $oints of our thermodynamic $ath are
fi)ed# the sing!e most im$ortant question is determining the path that !eads to such an end $oint This $ath
dictates *hether or not you ha"e the ma-imum recovery $ossib!e from the system
6hen *e ta!- about gas cyc!ing# *e are genera!!y referring to the $ractice of in9ecting gas bac- into the
reser"oir This is done in order to o$timi&e the thermodynamic path *e ha"e chosen to ta-e (n a ty$ica!
condensate system# you genera!!y $roduce a wet gas from the system *ith a high !iquid yie!d at the surface
At the surface# you $ass this gas through a series of se$arators, during this $rocess !iquid is going to dro$
out The !iquid that dro$s out *i!! be rich in the hea"ier com$onents 0ence# the gas that comes out of the
se$arator *i!! be dry (ie# "ery !ight) (f you in9ect this !ean gas bac- into the reser"oir# there *i!! be a
!eaching $rocess A!! you are trying to do from the $oint of "ie* of the $hase diagram is to mo"e the $hase
boundary and de* $oint to*ards the !eft (!o*er tem$eratures &ones) 5et me e)$!ain this in more detai!
5et us say that *e ha"e the $hase en"e!o$e for the reser"oir f!uid sho*n in 1igure 6<# *ith the gi"en $ath of
$roduction (f *e *ere to fo!!o* the $ath from (A # Tf) to (E # Tf)# *e *ou!d enter the t*o%$hase region and
end u$ ha"ing !iquid in the reser"oir 0o*e"er# you do not *ant !iquid in the reser"oir because its !o*
mobi!ity dictates that it *ou!d not be reco"ered^ +e)t# you *ant to mo"e that $hase diagram to the !eft by
in9ecting a !ighter gas 6hen you in9ect a !ighter gas# the $hase en"e!o$e shifts to the !eft, your $roduction
$ath *i!! be free of !iquid dro$out at reser"oir conditions 8y in9ecting the gas# *e are ma-ing the o"era!!
com$osition of the reser"oir f!uid !ighter The effect of com$osition on $hase beha"ior *as discussed in the
$re"ious modu!e (see 1igure O2 in Modu!e O) This e)am$!e demonstrates the im$ortance of $hase
diagrams as too!s that he!$ us $roduce a reser"oir in an o$tima! *ay
So# *e recogni&e that *e needed phase behavior data for this $articu!ar system The question no* is how
do *e get the data7 6e can co!!ect data in at !east t*o *ays= from !aboratory measurements and from fie!d
measurements 5ab e)$eriments are e)$ensi"e# and *e cannot ho$e to generate data for e"ery foreseeab!e
condition *e may encounter Lust to gi"e you an idea# generating a sing!e $hase en"e!o$e may cost at !east
b<20#000 This is not something you *ant to be doing a!! the time On the other hand# if you *ent to the fie!d#
you *ou!d !ose "a!uab!e resources or ha"e to sto$ o$erations to ma-e your obser"ations On a routine
basis# you don/t *ant to use the fie!d or a !ab as your main sources of $hase beha"ior data These o$tions
mean a !ot of !ost re"enue and a great dea! of e)$ense (s there a third o$tion7 ;es# indeed 6e can re!y on
prediction# by *hich *e $roduce a mode! that can do this *or- for us (n fact# *e *i!! be dea!ing *ith# and
de"e!o$ing# this o$tion in this course
The basis for such a mode! is *hat is ca!!ed an /quation of 0tate (EOS) 0ence# the centra! $art of this
course is EOS# since they are the basis of *hat *e do in $hase beha"ior
There are se"era! other e)am$!es that i!!ustrate "ery "i"id!y *hy *e need to study equations of state 1or
instance# !et us thin- about the conce$t of equi!ibrium
(n $etro!eum $roduction# *e genera!!y ma-e the assum$tion that# at e"ery stage# the system is in
equi!ibrium 6hen you thin- about equi!ibrium# you genera!!y thin- about a system that is static# that is# not
mo"ing 6hen a system is mo"ing# it cannot# in actua!ity# be in equi!ibrium +e"erthe!ess# the best a$$roach
*e ha"e so far is to describe it using equi!ibrium thermodynamics 6hi!e *e usua!!y assume equi!ibrium# *e
recogni&e that it is not a $erfect assum$tion# but that it is a reasonab!e one
This means that in the course of $roducing the reser"oir# a $rocess *hich a!*ays in"o!"es mo"ement# ( am
assuming that e"ery*here the gas and the !iquid are in equi!ibrium 6ith this assum$tion# *e are free to use
equi!ibrium thermodynamics# so *e are ab!e to em$!oy EOS in describing the state of the system
3onsider the reser"oir in 1igure 6<# in an entire!y gaseous condition at (A# Tf)# and ha"ing a -no*n f!uid
com$osition &ri (iB<#`n) As *e $roduce this reser"oir through a $i$e!ine# *e ta-e the f!uid from reser"oir
conditions through a battery of se$arators 4enera!!y s$ea-ing# *e dea! *ith a series of se$arators# but for
the sa-e of this discussion *e *i!! assume that *e ha"e 9ust a sing!e se$arator
This se$arator does not care about the $ressure and tem$erature of the reser"oir (t on!y cares about its o*n
$ressure and tem$erature condition= 's# Ts The com$osition of the f!uid at the se$arator in!et is assumed to
be the same as that of the reser"oir f!uid# a!though this is strict!y true on!y for sing!e $hase conditions
The f!uid e)its the se$arator in t*o streams= a "a$or stream and a !iquid stream As a $etro!eum engineer#
*e *ant to -no* ho* much gas# ho* much !iquid# and the qua!ity (com$ositions) of both streams That is#
*e need quantitati"e and qua!itati"e information As *e sha!! study in Modu!e <2# *e can $erform a materia!
ba!ance around each se$arator to ca!cu!ate the amount of "a$or and !iquid that is to be reco"ered 6e *i!!
need the $ro$erties of both streams (such as density and mo!ecu!ar *eight) in order to e)$ress f!o* rates in
suitab!e fie!d units
0o* do *e generate a!! this7 6e need a too!, that too! is an Equation of State^ 6hy do *e need an Equation
of State7 6e need EOS to define the state of the system and to determine the properties of the system at
that state That is *hy it is ca!!ed an equation of state As you may ha"e noticed# something critica! in this
series of !ectures is the abi!ity to estab!ish lin!s *ithin a!! the materia! *e are studying 6e *i!! not !oo- at
each to$ic sim$!y as an isolated compartment, but instead# *e must thin- in terms of ho* each $iece of
information fits into the o"era!! $icture that *e are de"e!o$ing
Part I
P!8!4 Behavior
6e embar- no* on a rather ambitious 9ourney 4i"en a f!uid# *e *ou!d !i-e to de"e!o$ mathematica!
re!ationshi$s for $redicting its beha"ior under any imaginab!e condition of $ressure# tem$erature and "o!ume
('%2%T) (n other *ords# *e *ant to describe the '%2%T beha"ior of fluids in genera!
As *e stated ear!ier# this is a "ery cha!!enging $rob!em The *ay science a$$roaches these sorts of
$rob!ems is to introduce sim$!ifications of the $hysica! rea!ity (n other *ords# *e formu!ate a set of
assum$tions and come u$ *ith a base mode! that *e might ca!! idea! 1rom that $oint on# once the base
mode! has been estab!ished# *e !oo- at a rea! case by estimating ho* c!ose (or far) it $erforms# *ith res$ect
to the base (idea!) case# and introducing the corres$onding corrections Such corrections *i!! ta-e into
account a!! the considerations that our origina! assum$tions !eft out
5et us discuss our base case for f!uids (the sim$!est f!uid *e may dea! *ith)= the idea! or $erfect gas
Part I
Ideal Behavior
An idea! gas is an imaginary gas that satisfies the fo!!o*ing conditions=
+eg!igib!e interactions bet*een the mo!ecu!es#
(ts mo!ecu!es occu$y no "o!ume (neg!igib!e mo!ecu!ar "o!ume)#
3o!!isions bet*een mo!ecu!es are $erfect!y e!astic . this is# no energy is !ost after co!!iding
6e recogni&e that this f!uid is imaginary because . strict!y s$ea-ing . there are no ideal gases (n any
f!uid# a!! mo!ecu!es are attracted to one another to some e)tent 0o*e"er# the ideal a$$ro)imation *or-s
best at some !imiting conditions# *here attraction forces can be considered to be *ea- (n fact# idea!
beha"ior may be a$$roached by real gases at low pressures (c!ose to atmos$heric) and high temperatures
+ote that at !o* $ressures and high tem$eratures# the distance bet*een any $air of gas mo!ecu!es is great
Since attraction forces *ea-en *ith distance# *e ha"e chosen a condition *here attraction forces may be
neg!ected (n conc!usion# *e consider a gas idea! *hen each mo!ecu!e beha"es as if it *ere a!one .
mo!ecu!es are so far a$art from each other that they are not affected by the e)istence of other mo!ecu!es
The beha"ior of idea! gases has been studied e)hausti"e!y and can been e)tensi"e!y described by
mathematica! re!ationshi$s
1or a gi"en mass of an idea! gas# "o!ume is in"erse!y $ro$ortiona! to $ressure at constant tem$erature# ie#
(at constant tem$erature) #/.1&
This re!ationshi$ is -no*n as 8oy!e/s 5a* Additiona!!y# "o!ume is direct!y $ro$ortiona! to tem$erature if
$ressure is -e$t constant# ie#
(at constant $ressure)#/.)&
This re!ationshi$ is -no*n as 3har!es/ 5a* 8y combining both !a*s and recogni&ing @:A (the uni"ersa! gas
constant) as the constant of $ro$ortiona!ity# *e end u$ *ith the "ery fami!iar equation=
#/.,&
This re$resents the equation of state (EOS) of an idea! gas +umerica! "a!ues of @:A de$end on the system
of units that is used=
(f *e construct the '%" diagram for an idea! gas at a gi"en tem$erature# *e end u$ *ith the isotherm sho*n
in 1igure 62
Figure /.): +8v Fsot!er" 9or an Fdeal Gas
The idea! gas mode! $redicts t*o !imiting f!uid beha"iors= first# that the "o!ume of the gas becomes "ery !arge
at "ery !o* $ressures (ie# as # a conce$t that agrees *ith *hat *e -no* from our
e)$erience in the $hysica! *or!d) And second# as (the "o!ume of matter 9ust @"anishesA if
the $ressure is high enough= this conce$t *e *ou!d not be as *i!!ing to acce$t) These t*o beha"iors are a
consequence of the assum$tions made in the idea! gas mode!
Part I
Real Gases
(n rea!ity# no gas beha"es idea!!y Therefore# the idea! EOS is not usefu! for $ractica! a$$!ications# a!though it
is im$ortant as the basis of our understanding of gas beha"ior E"en though the idea! mode! is not re!iab!e
for rea! engineering a$$!ications# *e ha"e to -ee$ in mind that the idea! gas EOS is the starting $oint of a!!
modern a$$roaches
(f *e !oo- bac- at 1igure 62 and reca!! our discussions about '%" beha"ior of $ure substances# something
shou!d catch your attention 1igure 6D sho*s us the ty$ica! '%" beha"ior of a $ure substance to faci!itate our
discussion
Figure /.,: +8v Fsot!er" 9or an Fdeal Gas
6hat can *e conc!ude about the idea! EOS *hi!e contrasting 1igure 62 to 6D7 The cur"e in 1igure 62 is
continuous, 1igure 6D has an ob"ious discontinuity (at the "a$orC!iquid transition) 0ence# one thing *e can
a!ready say is that the idea! EOS is at least qua!itati"e!y *rong 1or a rea! substance# as $ressure increases#
there "ust be a $oint of discontinuity that re$resents the $hase change 8deal gas will not condense, no
matter what pressure it is sub*ected to, regardless of the temperature of the system (n other *ords# *e
cannot ho$e to re$roduce the '%" beha"ior of 1igure 6D using the idea! equation (6D) since no discontinuity
is to be found 0o*e"er# the rea! '%" isotherm can be a$$ro)imated by idea! beha"ior at !o* $ressures# as
*e can see from the $!ots
6e can a!so estab!ish some quantitati"e differences bet*een idea! and rea! '2T beha"ior 1or e)am$!e# for
most conditions of interest at a gi"en "o!ume and tem$erature# the idea! gas mode! o"er%$redicts the
$ressure of the system=
'(dea! 4as F ':ea! 4as#/.-&
6e can e)$!ain this difference by reca!!ing that a rea! gas does ha"e interaction forces bet*een mo!ecu!es
Second!y# *e reca!! that the conce$t of @$ressureA of a gas is a consequence of the number of mo!ecu!ar
co!!isions $er unit area against the *a!! of the container Such number of co!!isions is# in turn# a measure of
the freedom of the mo!ecu!es to tra"e! *ithin the gas The idea! gas is a state of com$!ete mo!ecu!ar freedom
*here mo!ecu!es do not e"en -no* the e)istence of the others 0ence# a hy$othetica! idea! gas *i!! e)ert a
higher $ressure than a rea! gas at any gi"en "o!ume and tem$erature 6hen mo!ecu!es come together (rea!
gas)# it reduces the a"ai!ab!e free s$ace for the mo!ecu!es and $ressure is reduced
Additiona!!y# the idea! mode! assumes that the $hysica! s$ace that the mo!ecu!es themse!"es occu$y is
neg!igib!e (n rea!ity mo!ecu!es are $hysica! $artic!es and they do occu$y s$ace Once *e find a *ay of
accounting for the s$ace that the mo!ecu!es themse!"es occu$y# *e *ou!d be ab!e to com$ute a @rea!A free
"o!ume a"ai!ab!e for the mo!ecu!es to tra"e! through the gas (n the idea! case# this free "o!ume is equa! to
the "o!ume of the container itse!f since mo!ecu!ar "o!ume is not accounted for (n the rea! case# this free
"o!ume must be !ess than the "o!ume of the container itse!f after *e account for the $hysica! s$ace that
mo!ecu!es occu$y Therefore=
2rea!# free E 2(dea! B 23ontainer#/..a&
2rea!# free B 23ontainer S 2occu$ied by mo!ecu!es#/..b&
Part I
Summary
The idea! gas EOS is inaccurate both quantitati"e!y and qua!itati"e!y Tuantitati"e!y# idea! gas *i!! not
condense no matter *hat $ressure and tem$erature the system is sub9ected to Tuantitati"e!y# $ressures
and "o!umes used by the idea! gas mode! are higher than the "a!ues that a rea! gas *ou!d ha"e These are
the $rimary reasons that scientists ha"e made an effort to go beyond the idea! gas EOS# sim$!y because it
does not a$$!y for a!! the cases of interest
Part I
Action Item
for this modu!e
Please note:
date
Problem Set
< Qnder *hat conditions shou!d a rea! gas beha"e as an idea! gas7
2 3an *e manufacture an idea! gas7
D 6rite a $aragra$h on *hat you thin- *e shou!d do *ith the idea! gas equation to ma-e it a$$!icab!e
to rea! gases Mescribe a!! the considerations that you fee! must be accounted for
Part II
Module Goals
Module Objective: To introduce you to the conce$t of G%factor and the "an der 6aa!s equation of state
Part II
0!6actor
1rom the !ast modu!e# it is "ery !i-e!y that one question is !eft in our minds 0o* can *e ad9ust the idea!
mode! to ma-e it suitab!e for rea! gases7 6e!!# *e a!ready ha"e the ans*er 6e said that once *e ha"e
estab!ished a base )ideal+ model# *e !oo- at a rea! case by estimating ho* c!ose (or far) it $erforms *ith
res$ect to the base )ideal+ case, and introducing the corres$onding corrections Again# such corrections *i!!
ta-e into account a!! the considerations that our origina! assum$tions !eft out
1or the case of gas beha"ior# *e introduce a correction factor to account for the discre$ancies bet*een
e)$erimenta! obser"ations and $redictions from our ideal mode! This correction factor is usua!!y referred to
as the compressibility factor (G)# and is defined as=
#0.1&
(n the $re"ious equation# 9 is the rea! "o!ume occu$ied by the gas and 98deal is the "o!ume that the ideal
mode! $redicts for the same conditions The idea! "o!ume is gi"en by=
#0.)&
0ence# the equation of state for rea! gases is *ritten as=
#0.,&
Engineers are "ery much fami!iar *ith this equation# to the e)tent that it is usua!!y recogni&ed as
/ngineering /70 '!ease note that for G B <# this equation co!!a$ses to the ideal gas model (n fact# unity is
the com$ressibi!ity factor of any gas that beha"es idea!!y 0o*e"er# $!ease note that G B < is a consequence
of idea! beha"ior# but this is not a definition
o"et!ing to t!inK about:
(s it $ossib!e to ha"e a rea! gas at a condition at *hich GB< *ithout being idea! (far remo"ed from the idea!%
gas theory assum$tions)7
1or natura! gases# the most enduring method of estimating G has been the Hat&%Standing Method 0o*e"er#
*e are no* !i"ing in a com$uter%dri"en era# *here thermodynamic estimations are "ery rare!y ta-en from
gra$hs or $!ots# as *as common in the $ast
Part II
7e-inition o- E3uation o- State %ES)
Assuming an equi!ibrium state# the three $ro$erties needed to com$!ete!y define the state of a system are
$ressure (')# "o!ume (2)# and tem$erature (T) 0ence# *e shou!d be ab!e to formu!ate an equation re!ating
these D "ariab!es# of the form f('#T#2)B0
An equation of state (EOS) is a functiona! re!ationshi$ bet*een state "ariab!es . usua!!y a com$!ete set of
such "ariab!es Most EOS are *ritten to e)$ress functiona! re!ationshi$s bet*een '# T and 2 (t is a!so true
that most EOS are sti!! em$irica! or semi%em$irica! 0ence# the definition=
An E:uation o9 tate #EO& is a semi%em$irica! functiona! re!ationshi$ bet*een $ressure# "o!ume and
tem$erature of a $ure substance 6e can a!so a$$!y an EOS to a mi)ture by in"o-ing a$$ro$riate mi)ing
ru!es
There ha"e been a number of attem$ts to deri"e a theoretica!!y sound EOS, but# genera!!y s$ea-ing# not
much success has been achie"ed a!ong that !ine As a resu!t# *e use *hat are -no*n as semi%em$irica!
EOS Most equations of state used today are semi%em$irica! in nature# this being so because they are fitted
to data that are a"ai!ab!e Additiona!!y# equations of state are genera!!y de"e!o$ed for $ure substances Their
a$$!ication to mi)tures requires an additiona! "ariab!e (com$osition) and hence an a$$ro$riate mi)ing ru!e
The functiona! form of an EOS can be e)$ressed as=
#0.-&
*here a- B EOS $arameters
As *e stated ear!ier# most a$$!icab!e EOS today are semi%em$irica!# in the sense that they ha"e some
theoretica! basis but their $arameters (a-) must be ad9usted The number of $arameters (n$) determines the
category>com$!e)ity of the EOS 1or instance# <%$arameter EOS are those for *hich n$ B <# and 2%
$arameter EOS are those for *hich n$ B 2 The higher @n$A is# the more com$!e) is the EOS A!so# in genera!
terms# the more com$!e) the EOS# the more accurate it is 0o*e"er# this is not a!*ays the case, in some
cases a rather sim$!e EOS can do a "ery good 9ob
Since the time of the idea! gas !a* (idea! gas EOS)# a great number of equations of state ha"e been
$ro$osed to describe rea! gas beha"ior 0o*e"er# many of those ha"e not $assed the test of time On!y fe*
ha"e $ersisted through the years# this because of their re!ati"e sim$!icity (n the $etro!eum business# the
most common modern EOS are the 'eng :obinson EOS (': EOS) and Soa"e%:ed!ich%H*ong EOS (S:H
EOS) 8oth of these are cubic EOS and hence deri"ations of the "an der 6aa!s EOS# *hich *e *i!! be
discussing ne)t There are other more com$!e) EOS# a!though they ha"e not yet found *ides$read
a$$!ication in our fie!d=
5ee Hes!er EOS (5H EOS)
8enedict%6ebb%:ubin EOS (86: EOS)
8enedict%6ebb%:ubin%Star!ing EOS (86:S EOS)
(n the natura! gas business# es$ecia!!y in the gas transmission industry# the standard EOS used is the A4A
EOS, this is an u!tra%accurate EOS for G%factor ca!cu!ations . a "ery sensiti"e "ariab!e for custody%transfer
o$erations
Part II
Purpose and 9istorical 7evelopment
6e *ant to use EOS as the basis for generating data= "o!umetric data# thermo$hysica! data# and to he!$ us
$erform "a$or>!iquid equi!ibrium (25E) ca!cu!ations 'robab!y there has not been an area of thermodynamics
to *hich so many hours of research ha"e been de"oted as that of the to$ic of EOS Among the $ro$erties
deri"ed from an EOS inc!ude=
Mensities ("a$or and !iquid)#
2a$or $ressures of $ure com$onents#
3ritica! $ressures and tem$eratures for the mi)ture#
2a$or%5iquid equi!ibrium (25E) information#
Thermodynamic $ro$erties (c0# cS# c4# cA)
233 %ears o EOS ,evelopment
+ERFO> 1: BFoundational 4orKC
4efore $&&", there was an incomplete understanding and qualitative representation of the volumetric
behavior of gases.
<662= 1irst brea-through . 8oy!e/s 5a* 8oy!e did not define an idea! beha"ior 6hen he $ro$osed this !a*#
he *as con"inced that it a$$!ied to a!! gases Among the !imitations that 8oy!e *as *or-ing under= no high
$ressure measurements cou!d ha"e been ta-en using the equi$ment of his time# and his *or-ing f!uid *as
air 0ence# it is no *onder that e"erything these $ioneers did $ertained to *hat *e no* recogni&e as the
idea! state
'2 Bconstant
<K8K= 3har!es/ 5a* (t *as one hundred $!us years unti! a ne*# im$ortant de"e!o$ment in the gas beha"ior
fie!d 3har!es $ostu!ated that the "o!ume of a gas is $ro$ortiona! to its tem$erature at isobaric conditions
3ombining# '2>T B constant B :# gas constant
<80<= Ma!ton introduced the conce$t of $artia! $ressures and recogni&ed that the tota! $ressure of a gas is
the sum of the indi"idua! ($artia!) contributions of its constituents
<802= 4ay%5ussac 0e he!$ed to define the universal gas constant @:A Ma!ton had !oo-ed at different gases
and ca!cu!ated the ratio '2>T to "erify that it *as constant 0o*e"er# it *as be!ie"ed that each gas may ha"e
its o*n : 4ay%5ussac sho*ed that a sing!e constant a$$!ied to a!! gases# and ca!cu!ated the @uni"ersa!A gas
constant
<822= 3agniard de !a Tour 0e disco"ered the critica! state (critica! $oint) of a substance
<8DJ= 3!a$eyron 0e *as the first to suggest '2B:(TC2KD)
+ERFO> ): BMonu"ental <orKC
Period of turning points and landmar!s with quantitative developments.
<8KD= "an der 6aa!s 6ith "an der 6aa!s# a quantitati"e a$$roach *as ta-en
for the first time 0e *as an e)$erimenta!ist and $ro$osed the continuity of gases and !iquid that *on for him
a +obe! 'ri&e 0e has $ro"ided the most im$ortant contribution to EOS de"e!o$ment
<8KO= 4ibbs# an American mathematica! $hysicist# made the most im$ortant contributions to the
thermodynamics of equi!ibrium in *hat has been recogni&ed as a monumenta! *or-
<I0<= Onnes theoretica!!y confirmed the critica! state
<I02= 5e*is defined the conce$t of fugacity
<I2K= Qrse!! $ro$osed a series so!ution ($o!ynomia! functiona! form) for EOS= ' B < C b>2 C c>22 C d>2D C`
This is -no*n as the "iria! EOS 2iria! EOS has better theoretica! foundation than any other 0o*e"er# cubic
EOS (as "d6/s) need on!y 2 $arameters and ha"e become more *ides$read in use
+ERFO> ,: BFncre"ental F"prove"entC
.uring this last and current period, a better quantitative description of volumetric behavior has been
achieved at a rather low pace. :hat is stri!ing, as we will study later, is that most of the tools of most critical
use for us today are based on the wor!s of van der :aals, 3ibbs, and ;ewis, and have been around for
years
<IJ0= 8enedit# 6ebb# [ :ubbin $ro$osed *hat can be ca!!ed the @3adi!!acA of EOS# ie# the most
so$histicated and most accurate for some systems 0o*e"er# the $rice to $ay is that it is com$!icated and
not easy to use
<IJI= :ed!ich [ H*ong introduced a tem$erature de$endency to the attraction $arameter @aA of the "d6
EOS
<IOO= 'it&er introduced the idea of the @acentric factorA to quantify the non%s$hericity of mo!ecu!es and *as
ab!e to re!ate it to "a$or $ressure data
<IK2= Soa"e modified the :H EOS by introducing 'it&er/s acentric factor
<IK6= 'eng and :obinson $ro$osed their EOS as a resu!t of a study s$onsored by the 3anadian 4as
3ommission# in *hich the main goa! *as finding the EOS best a$$!icab!e to natura! gas systems
Since then# there has not been any radica! im$ro"ement to S:H and ': EOS# a!though a great dea! of *or-
is sti!! under*ay
Part II
4he van der Waals E3uation
E"en though "an der 6aa!s EOS ("d6 EOS) has been around for more than one hundred years# *e sti!!
recogni&e "an der 6aa!s/ achie"ements as crucia! in re"o!utioni&ing our thin-ing about EOS 6e ta!- about
"d6 EOS because of $edagogica! reasons# not because it finds any $ractica! a$$!ication in today/s *or!d (n
fact# "d6 EOS is not used for any $ractica! design $ur$oses 0o*e"er# most of the EOS being used *ide!y
today for $ractica! design $ur$oses ha"e been deri"ed from "d6 EOS
The contributions of "d6 EOS can be summari&ed as fo!!o*s=
(t radica!!y im$ro"ed $redicti"e ca$abi!ity o"er idea! gas EOS#
(t *as the first to $redict continuity of matter bet*een gas and !iquid#
(t formu!ated the 'rinci$!e of 3orres$onding States ('3S)#
(t !aid foundations for modern cubic EOS
(n his 'hM thesis in <8KD# "an der 6aa!s $ro$osed to semi%em$irica!!y remo"e the main -ey @*ea-nessesA
that the idea! EOS carried *ith it Essentia!!y# *hat he did *as to !oo- again at the basic assum$tions that
under!ie the idea! EOS# *hich *e ha"e !isted abo"e
"d6 accounted for the non%&ero mo!ecu!ar "o!ume and non%&ero force of attraction of a rea! substance 0e
rea!i&ed that there is a $oint at *hich the "o!ume occu$ied by the mo!ecu!es cannot be neg!ected One of the
first things "d6 recogni&ed is that mo!ecu!es must ha"e a finite "o!ume# and that "o!ume must be subtracted
from the "o!ume of the container At the same time# he modified the $ressure term to ac-no*!edge the fact
that mo!ecu!es do interact *ith each other though cohesi"e forces These are the t*o main "a!uab!e
recognitions that he introduced
The idea! EOS states=
#0..&
or#
#0./&
*here re$resent the mo!ar "o!ume ( ) of the substance
"d6 focused his attention on modifying the terms @'A and @"A in the origina! idea! gas !a* by introducing an
a$$ro$riate correction 5oo-ing bac- at the inequa!ity of equation (6J) in Modu!e 6# "d6 $ro$osed that the
difference of both $ressures is the resu!t of the attraction forces . cohesi"e forces . neg!ected in the idea!
mode! (equation K6) and thus#
#0.0&
At this $oint# "d6 $ostu!ated the term N'attraction# an in"erse function of the mean distance bet*een
mo!ecu!es . this being a direct consequence of +e*ton/s !a* of inertia! attraction forces# 1 a (distance)
%2

:ecogni&ing that the "o!ume of the gas is a measure of the mean distance bet*een mo!ecu!es (the sma!!er
the "o!ume# the c!oser the mo!ecu!es and "ice "ersa)#
#0.1&
and using @aA as a constant of $ro$ortiona!ity#
#0.2&
+e)t# "d6 too- care of the inequa!ity in equation (6O) (see Modu!e 6) Any $artic!e occu$ies a $hysica!
s$ace, hence# the s$ace a"ai!ab!e to the gas is !ess than the tota! "o!ume of its container 5et us say *e can
e)$erimenta!!y determine the actua! $hysica! s$ace that a!! the mo!ecu!es in the container occu$y# and that
*e ca!! it @bA# or the co%"o!ume "d6 then $ro$osed=
#0.10&
The inc!usion of a $arameter @bA (co%"o!ume) recogni&es the ro!e of re$u!si"e forces :e$u!si"e forces
$re"ent mo!ecu!es from @destroyingA one another by not !etting them get too c!ose (n a condensed state#
there is a ma)imum a!!o*ab!e @c!osenessA among mo!ecu!es Therefore# it is because of re$u!si"e forces
that *e cannot com$ress the "o!ume of a f!uid beyond its co%"o!ume "a!ue @bA (f the mo!ecu!es get too c!ose
to each other# re$u!sion forces ta-e o"er to $re"ent their se!f%destruction
(n summary# "d6 $ro$osed to correct the $ressure and "o!ume terms of the idea! mode! re$resented by
equation (K6) The @ne*A modified%idea! equation of state becomes=
#0.11a&
or#
#0.11b&
*here=
' B abso!ute $ressure
" B mo!ar "o!ume
T B abso!ute tem$erature
: B uni"ersa! gas constant
Equation (K<<b) demonstrates that "d6 EOS is e)$!icit in $ressure At this stage it is im$ortant to stress
that any $rediction for from equations (K<<) is meaning!ess due to the $hysica! significance that *e
ha"e attached to this $arameter Since a!! the others $arameters are constants# equations (K<<) are
functiona! re!ationshi$s of the "ariab!es '# T and =
#0.1)&
Therefore# equation (K<<a) e)$resses a '2T re!ationshi$ and hence# it is an equation of state (n this
equation# @aA and @bA are constants that are s$ecific to each com$onent 0o*e"er# the numerica! "a!ue of @:A
de$ends on the system of units chosen# as *e discussed abo"e
(t is time to as- ourse!"es a "ery im$ortant question=
How do we calculate <a= and <b= for each substance>
As can be inferred from their definitions# @aA and @bA are different for different substances, ie#
,
0o* do *e re!ate @aA and @bA to *e!!%-no*n and easi!y%obtainab!e $hysica! $ro$erties of substances7
(t turns out that there are a set of conditions ca!!ed criticality conditions that must be satisfied for a!! systems#
$ro"ided that those systems satisfy the 2
nd
!a* of thermodynamics (ndeed# in the $re"ious cha$ter *e
recogni&ed that the critica! isotherm of a $ure substance has a $oint of inf!e)ion (change of cur"ature) at the
critica! $oint 1urthermore# *e recogni&ed the critica! $oint to be the ma)imum $oint (a$e)) of the '%2
en"e!o$e This condition of hori&onta! inf!e)ion of the critica! isotherm at the critica! $oint is mathematica!!y
im$osed by the e)$ression=
#0.1,&
These conditions are ca!!ed the criticality conditions. (t turns out that *hen one im$oses these conditions on
equation (K<<a)# one is ab!e to deri"e e)$ressions for the $arameters @aA and @bA as a function of critica!
$ro$erties as fo!!o*s=
#0.1-a&
#0.1-b&
;ou may *ant to $ro"e this as an e)ercise @aA and @bA can therefore be -no*n because they are functions
of -no*n (tabu!ated) $ro$erties of a!! substances of interest (critica! $ressure and tem$erature)
So far# *e ha"e a$$!ied "d6 EOS to $ure com$onents 3an *e e)tra$o!ate this to a$$!y to mu!ti%com$onent
systems7
To e)tend this conce$t to a system of more than one com$onent# *e use *hat is ca!!ed a mi-ing rule. A
mi)ing ru!e re!ates the $arameters that characteri&e the mi)ture (am and bm) to the indi"idua! contributions of
the $ure com$onents that ma-e u$ that mi)ture (ai and bi)
0o* do *e do this7 "d6 $ro$osed to *eight the contributions of each com$onent using their mo!e
com$ositions# as fo!!o*s=
#0.1.a&
#0.1.b&
The former is ca!!ed the quadratic mi)ing ru!e# *hi!e the !atter is -no*n as the !inear mi)ing ru!e
Part II
Action Item
for this modu!e
Please note:
date
Problem Set
< (f a gas is idea!# *ou!d its com$ressibi!ity factor (G) be a!*ays equa! to one7
2 1or a gas *ith GB<# *ou!d its beha"ior be idea!7
D Ta-e a !oo- at the Standing%Hat& 3om$ressibi!ity 1actor '!ot for +atura! 4ases 6hat is the
information you need to obtain a "a!ue of @GA for a gas7 6hat ha$$ens to @GA at !o* $ressures7
6hat is the beha"ior of @GA at high $ressures7 6hat is the com$ressibi!ity factor of Methane ('c B
666 $sia# Tc B S <<K 1) at ' B <000 $sia and T B 0 17
J As $ressure a$$roaches to &ero# *hat shou!d "d6 EOS co!!a$se to7 6hy7 3an you sho* it7
O S$ecu!ate on ho* you cou!d ca!cu!ate the @GA factor for a gas using "d6 EOS
Part III
Module Goals
Module Objective: To high!ight the $rinci$!e of corres$onding states and its im$ortance for
thermodynamic corre!ations
Part III
Principle o- Correspondin$ States %PCS)
The $rinci$!e of 3orres$onding States ('3S) *as stated by "an der 6aa!s and reads= @Substances beha"e
a!i-e at the same reduced states Substances at same reduced states are at corres$onding statesA That is#
<0ubstances at corresponding states behave ali!e.=
:educed $ro$erties are used to define corres$onding states :educed $ro$erties $ro"ide a measure of the
@de$artureA of the conditions of the substance from its o*n critica! conditions and are defined as fo!!o*s=
#1.1a&
#1.1b&
#1.1c&
(f 'r B Tr B "r B <# the substance is at its critica! condition (f *e are beyond critica! conditions# Tr F <# 'r F <
and "r F < 8y the same to-en# if a!! the conditions are subcritica!# Tr E <# 'r E < and "r E < 3ritica! conditions
become the sca!ing factor by *hich substances can be com$ared among each other in terms of their
@de$arture from critica!ityA or reduced $ro$erties
The '3S says that a!! gases beha"e a!i-e at the same reduced conditions That is# if t*o gases ha"e the
same @re!ati"e de$artureA from critica!ity (ie# they are at the same reduced conditions)# the corres$onding
state $rinci$!e demands that they beha"e a!i-e (n this case# the t*o conditions @corres$ondA to one another#
and *e are to e)$ect those gases to ha"e the same $ro$erties
The 3orres$onding State 'rinci$!e can be deri"ed from "d6 EOS (f *e reca!!#
#1.)a&
*here=
#1.)b&
#1.)c&
6e defined the reduced conditions as=
#1.,&
(f *e substitute a!! this into "d6 EOS#
#1.-&
Sim$!ifying the e)$ression# and em$!oying the e)$ressions=
#1..a&
#1..b&
6e get=
#1./&
Equation (86) is the reduced form of "d6 EOS See ho* this equation is @uni"ersa!A (t does not care about
*hich f!uids *e are ta!-ing about Lust gi"e it the reduced conditions @'r# TrA and it *i!! gi"e you bac- "r .
regard!ess of the f!uid 0ence# if you com$ute "r for a certain f!uid by entering 'r and Tr for that f!uid into "d6
reduced EOS (equation 86)# you *i!! com$ute the same "r# for any other f!uid at the same conditions of 'r
and Tr There is no other $ossibi!ity Strict!y s$ea-ing# "an der 6aa!s/ 3orres$onding States 'rinci$!e reads=
@fluids at the same reduced pressures and temperatures have the same reduced volumeA This is ho* "an
der 6aa!s disco"ered the 'rinci$!e of 3orres$onding States As !ong as t*o gases are at corres$onding
states (same reduced conditions)# it does not matter *hat com$onents you are ta!-ing about# or *hat is the
nature of the substances you are ta!-ing about, they *i!! beha"e a!i-e
The critica! $oint $ro"ides the $erfect sca!ing for the a$$!ication of the corres$onding state $rinci$!e because
of the e)istence of the criticality conditions (n fact# equation (K<D) XModu!e KY ma-es the a$$!ication of
corresponding states $ossib!e for equations of state
#0.1,&
(ndeed# for us to arri"e at equation (86)# *e needed to use equations (82) . *hich in turn *ere the
outcome of the a$$!ication of the criticality conditions to "an der 6aa!s/ equation of state As a resu!t# gases
that ha"e the same re!ati"e de$arture from their o*n critica! condition ha"e the same $ro$erties
6hat is the use of this $rinci$!e7 8asica!!y# it is used for thermodynamic corre!ations . its most $o*erfu!
a$$!ication Most thermodynamic corre!ations ha"e been made "iab!e and genera! because of the
a$$!ication of the $rinci$!e of corres$onding states An e)ce!!ent e)am$!e is the $o$u!ar G%chart of Standing
and Hat&# sho*n in 1igure 8< (n fact# most of the corre!ations that *e use in thermodynamics are based on
this $rinci$!e This e)$!ains *hy @'rA and @TrA so often a$$ear in thermodynamic corre!ations The main
reason for using @'rA and @TrA is to obtain the most genera!i&ed corre!ation $ossib!e# so that it is suitab!e for
use *ith most substances
Figure 1.1: tanding83at= Co"pressibilit* Factor C!art
#Re9erence: tanding and 3at=; $rans. 6FME; 12-)&
Part III
Acentric 6actor and Correspondin$ States
(t is im$ortant to $oint out that the '3S that *e ha"e 9ust discussed *as origina!!y out!ined by "an der
6aa!s (n rea!ity# it is the sim$!est "ersion of the $rinci$!e of corres$onding states# and it is referred to as the
two1parameter P,0 This is because it re!ies on t*o $arameters (reduced $ressure and tem$erature) for
defining a @corres$onding stateA
6ith the $assing of time# more accurate '3S formu!ations ha"e made use of more than t*o $arameters 1or
instance# the three%$arameter '3S affirms that t*o substances are in corres$onding states not on!y *hen
they are at the same reduced conditions (reduced $ressure and tem$erature)# but a!so *hen they ha"e the
same @acentric factorA "a!ue (n any case# the genera! statement of '3S remains untouched=
<0ubstances at corresponding states behave ali!e.=
6hat ma-es the difference is the definition of @*hat a corres$onding state isA
The acentric factor @*A is a conce$t that *as introduced by 'it&er in <IOO# and has $ro"en to be "ery usefu!
in the characteri&ation of substances (t has become a standard for the $ro$er characteri&ation of any sing!e
$ure com$onent# a!ong *ith other common $ro$erties# such as mo!ecu!ar *eight# critica! tem$erature# critica!
$ressure# and critica! "o!ume
'it&er came u$ *ith this factor by ana!y&ing the "a$or $ressure cur"es of "arious $ure substances 1rom
thermodynamic considerations# the "a$or $ressure cur"e that *e studied in our first modu!es for $ure
com$onents can be mathematica!!y described by the 3!ausius 3!a$eyron equation=
#1.0&
The use of the integrated "ersion of equation (8K) is "ery common for the mathematica! fitting of "a$or
$ressure data The integrated "ersion of equation (8K) sho*s that the re!ationshi$ bet*een the !ogarithm of
"a$or $ressure and the reci$roca! of abso!ute tem$erature is appro-imately !inear That is# in terms of
reduced conditions# "a$or $ressure data a$$ro)imate!y fo!!o*s a straight !ine *hen $!otted in terms of @!og'rA
"ersus @<>TrA# or# equi"a!ent!y=
#1.1&
(f the t*o%$arameter corres$onding state $rinci$!e *ere to ho!d true for a!! substances# the $arameters @aA
and @bA shou!d be the same for a!! substances That is# a!! "a$or $ressure cur"es of a!! imaginab!e
substances shou!d !ie on to$ of each *hen $!otted in terms of reduced conditions Stated in another *ay# if
the $!ot is of the form @!og'rA "ersus @<>TrA# a!! !ines shou!d sho* the same s!o$e (a) and interce$t (b)
The bad ne*s is that# as you may imagine# this is not a!*ays true 2a$or $ressure data for different
substances do fo!!o* different trends The good ne*s is that some gases fo!!o* the e)$ected trend 6hich
are they7 The nob!e gases +ob!e gases (such as Ar# Hr and de) ha$$en to fo!!o* the t*o%$arameter
corres$onding states theory "ery c!ose!y 0ence# they yie!d themse!"es amenab!e to acting as a reference to
e"a!uate @com$!ianceA *ith the t*o%$arameter equation of state
'it&er *anted to come u$ *ith a re!iab!e *ay of quantifying the de"iation of substances *ith res$ect to t*o%
$arameter corres$onding state $redictions 0e decided to use nob!e gases as the base for com$arison
Ana!y&ing "a$or $ressure data for nob!e gases# 'it&er sho*ed that a "a!ue of !og'r B S < *as achie"ed at
a$$ro)imate!y Tr B 0K So# 8(+4O^ There you are^ 0e thought= if the "a$or $ressure data of a substance
sho* that !og'r B S < at Tr B 0K# it beha"es as the nob!e gases and thus com$!ies *ith the t*o%$arameter
corres$onding states (f not# *e are to com$ute the difference=
#1.2&
'it&er ca!!ed this difference the @acentric factor# eA of the substance +ob!e gases# being the reference
themse!"es# ha"e an acentric factor "a!ue of &ero (eB0) Substances *ith an acentric factor of &ero are
ca!!ed @sim$!eA substances The acentric factor is said to be a measure of the non%s$hericity (acentricity) of
the mo!ecu!es Therefore# the three%$arameter corres$onding state theory of 'it&er reads= @1!uids that ha"e
the same "a!ue of e *i!! beha"e a!i-e at the same conditions of reduced $ressure and tem$eratureA
Part III
Action Item
for this modu!e
Please note:
date
Problem Set
< 3onsider Methane ('c B 666 $sia# Tc B S <<K 1) and Ethane ('c B K06 $sia# Tc B S I0 1) stored in
t*o different "esse!s at the fo!!o*ing conditions=
Methane 2esse! ' B <DD2 $sia T B OO 1
Ethane 2esse! ' B <J<2 $sia T B IO 1
2 Qsing the Standing%Hat& G%factor $!ot# determine the com$ressibi!ity factor of both substances Any
obser"ation7 Are those "a!ues different7 Mescribe the situation for both gases (f their G%factors are
the same# does it mean that both gases ha"e the same density7 6hat does it mean7
Module Cubic EOS and Their Behavior (I)
Module Goals
Module Objective: To introduce you to the basis $remises of cubic EOS and their beha"ior
Introduction
(f *e mu!ti$!y the "d6 EOS (e)$ression K<<a in Modu!e K) by and e)$and the factori&ed $roduct by
a$$!ying the distributi"e !a*# the resu!t is the "d6 EOS e)$ressed in terms of mo!ar "o!ume# as fo!!o*s=
#2.1&
+ote that equation (I<) is a third order $o!ynomia! in ie# it is cubic in mo!ar "o!ume Additiona!!y# *e can
substitute the definition of com$ressibi!ity factor G#
#2.)&
into equation (I<) and obtain a different cubic $o!ynomia! in G# as sho*n=
#2.,&
As *e see# "d6 EOS is referred to as cubic because it is a $o!ynomia! of order D in mo!ar "o!ume (and
hence in com$ressibi!ity factor G) (n genera!# any equation of state that is cubic in "o!ume (and G) and
e)$!icit in $ressure (equation K<<b) is regarded as a cubic equation of state "d6 EOS is a cubic EOS# and
a!! the transformations and modifications that it has undergone during the more than one hundred years
since its $ub!ication are a!so cubic /70? or better# they are in%the%"an%der%6aa!s%s$irit EOS or of%the%"an%
der%6aa!s%fami!y EOS
4he Cubic Behavior
5et us see *hat *e ha"e accom$!ished thus far 1irst# remember that *e are not satisfied *ith the fact that
the idea! gas !a* is not ab!e to $redict the discontinuity of 1igure 6D# *hich corres$onds to the condensation
that an a!!%gas $ure substance undergoes during isotherma! com$ressionThe isotherm that *e get from the
idea! mode! *as sho*n in 1igure 62 3ondensation# as *e -no*# is to be e)$ected at some $oint *hen you
isotherma!!y com$ress any $ure gas *hi!e be!o* its critica! conditions (T E Tc) This !ac- of conformance to
actua! beha"ior !ed us to rea!i&e that the idea! mode! is quantitati"e!y and qua!itati"e!y *rong at high
$ressures To remo"e the *ea-nesses of the idea! mode!# *e reca!! that "d6# in de"e!o$ing his equation of
state (equation K<<)# introduced the conce$ts of co%"o!ume and the attraction term
+o*# *e *onder# *hat did he rea!!y accom$!ish7 Are *e no* ab!e to $redict the condensation $henomena7
Are these @ne*A cubic%ty$e EOS ca$ab!e of sho*ing *here such a discontinuity occurs7 So far# *e ha"e not
seen *hat a cubic isotherm !oo-s !i-e 5et us $!ot the cubic isotherm for conditions be!o* critica! (T E Tc)#
su$erim$ose it on 1igure 6D# and see *hat *e get
Figure 2.1: +8v Fsot!er" 9or a cubic EO
1igure I< sho*s a ty$ica! cubic beha"ior That is# around condensation conditions# the equation of state
$resents an S%sha$ed cur"e This shou!d not come as a sur$rise, because the equation is cubic in "o!ume# it
*i!! $ro"ide three roots for "o!ume# and hence the S%sha$ed cubic feature 1or the sa-e of our discussion#
*e ha"e sho*n the gas and !iquid branches of the cubic equation !ying direct!y on to$ of the e)$erimenta!
ones This -ind of matching is the @u!timate goa!A of any cubic EOS# but in rea!ity# the matching is not this
good . es$ecia!!y for the case of the origina! "d6 EOS# as *e *i!! discuss !ater
The cubic beha"ior is bounded by the t*o e)tremes of rea! f!uid beha"ior# gi"en by the &ero $ressure and
infinite $ressure !imits On one hand# it is c!ear from equation (K<<b) that *e ha"e a singu!arity at #
*here @bA re$resents the co%"o!ume# or $hysica! s$ace that mo!ecu!es themse!"es occu$y This singu!arity
con"enient!y creates an asym$totic beha"ior (high $ressure asym$tote) of the cubic equation !iquid branch#
by *hich as :eca!! from our $re"ious discussions that $redictions for are
meaning!ess According!y# *e need an infinite amount of $ressure if *e are to com$ress a f!uid to the e)tent
that no free s$ace is a"ai!ab!e among mo!ecu!es ( ) On the other hand# it is c!ear from "d6 EOS
(equation K<<a) that as ( )# the cubic EOS co!!a$ses to the idea! EOS (equation K6) At this
!o* $ressure !imit# "d6
corrections to the idea! mode! become inconsequentia! ( # )
Mathematica!!y# this is the !o*%$ressure asym$tote of the cubic%equation gas branch by *hich as
5et us see ho* @goodA the cubic beha"ior is for the idea!%gas mode! :efer to 1igure I2# *here *e ha"e
su$erim$osed the idea! gas isotherm of 1igure 62 on the cubic EOS beha"ior
Figure 2.): +8v Fsot!er"s 9or t!e ideal gas EO and cubic EO
A !oo- at 1igure I2 he!$s us confirm that the cubic equation of state co!!a$ses to the $rediction of the idea!
gas mode! at reduced $ressure . ie# they share the same !o*%$ressure asym$tote This is to be e)$ected#
since the assum$tions under!ying the idea! mode! are satisfied As *e reca!!# these assum$tions are that the
attracti"e forces bet*een mo!ecu!es are "ery *ea- and that the $hysica! "o!ume of the mo!ecu!es can be
disregarded *hen com$ared to the tota! "o!ume of the container (t is *orthy to note that the high $ressure
asym$tote is not the same for both mode!s, as # as for the cubic mode! *hi!e for the
idea! mode! The !atter is a direct consequence of neg!ecting the mo!ecu!ar "o!ume in the idea! mode!
Implications o- S!shaped curve %Sub!critical Conditions)
A ma9or issue that has -e$t us banging our heads has been ho* to mathematica!!y re$resent the
discontinuity of the '%" isotherm during the "a$or%!iquid transition (1igure 6D) Such a discontinuity sho*s
u$ during the isotherma! com$ression of any $ure substance at sub%critica! conditions (T E Tc) 6hat *e
*ant here requires fitting a continuous mathematica! function to a discontinuous# rea!%!ife e"ent Strict!y
s$ea-ing# it *ou!d be contradictory to find a sing!e continuous mathematica! function that can ca$ture such a
discontinuity in its fu!! nature
3an *e rea!!y mode! the discontinuity7 +ot rea!!y# but *e can get around it "an der 6aa!s $ro"ided a
$ossib!e so!ution in his dissertation on the @continuity of "a$or and !iquidA E"en though neither cubic
equations nor any other continuous mathematica! function is ab!e to fo!!o* the discontinuity# *hat they can
do is good enough for engineering $ur$oses The @cubic beha"iorA can reasonab!y match the !iquid and
"a$or branches for the rea!# e)$erimenta! isotherms
Since "an der 6aa!s/ EOS# *e ha"e been ab!e to consider the continuity bet*een gas and !iquid $hases
+o*# *e need to !earn ho* to dea! *ith the S%sha$ed beha"ior# and to !oo- at it as a minor# inconsequentia!
$rice that *e $ay for the mode!ing of the "a$or . !iquid discontinuous transition *ith a continuous
mathematica! function 5et us &oom in on 1igure I<# as sho*n in 1igure ID
Figure 2.,: 8s!aped Feature o9 Cubic E:uations
There are se"era! features of the S%sha$ed beha"ior that shou!d be noted
( The S%sha$ed transition re$resents the &one *here gas and !iquid coe)ist in equi!ibrium for a $ure
substance, hence# such a beha"ior *i!! sho* u$ *hene"er a cubic equation of state is used for
$redictions at tem$eratures be!o* critica! conditions (sub%critica! conditions)
(( 'hysica!!y# changes in $ressure and changes in "o!ume in a f!uid must ha"e different signs in any
isotherma! $rocess# such that=
X Mechanica! Stabi!ity 3ondition Y
This requirement is met by the !iquid branch# gas branches and sections AA/ and 88/ of the cubic
isotherm 'ortions AA/ and 88/ ha"e e"en been rea!i&ed e)$erimenta!!y for metastab!e conditions#
ie# conditions of fragi!e or *ea- stabi!ity 0o*e"er# changes of $ressure and "o!ume ha"e the
same sign in $ortion A/8/, consequent!y# this $ortion of the cubic isotherm is regarded as
meaning!ess and un$hysica!
((( 'oint A/ and 8/ are the minimum and ma)imum "a!ues of the metastab!e beha"ior re$resented by
the S%sha$ed cur"e The saturation $ressure ('
sat
) *i!! natura!!y !ie bet*een these t*o e)tremes
4ra$hica!!y# '
sat
can be attained as the $ressure that ma-e the areas AoA/ and 8o8/ equa! This
equa!%area ru!e is -no*n as the Ma)*e!! $rinci$!e Simi!ar!y# *e can a!so determine the saturation
condition as the $ressure *here fugacity . a thermodynamic $ro$erty *e *i!! be studying !ater .
is equa! both at the !iquid and "a$or branches
(2 (t is not im$ossib!e for section AA/ of the cubic isotherm to reach negati"e $ressures (ie# 'A/ E 0)
This shou!d not be of any concern to us because *e are se!dom interested in such metastab!e
beha"ior (n fact# once '
sat
is determined# most $ractica! a$$!ications ca!! for c!eaning u$ the cubic
isotherm and su$$ressing areas AoA/ and 8o8/ (n this case# *e are !eft *ith !iquid branch# the
discontinuity A8/ at 'sat# and the gas branch, 9ust as the e)$erimenta! isotherm *ou!d !oo-
2 The most crucia! im$!ication of the S%sha$ed cur"e is that the cubic equation *i!! certain!y $roduce
three distinct rea! roots for mo!ar "o!ume (or com$ressibi!ity factor# if it is the case) This *i!! a!*ays
be the case as !ong as you are ma-ing a $rediction *ithin the S%sha$ed cur"e ('A/ E ' E '8/ , T E
Tc) At the "a$or%!iquid discontinuous transition . ie# at the interce$t of the cubic isotherm *ith the
saturation $ressure# '
sat
# at the gi"en tem$erature . *e end u$ *ith D mathematica!!y $ossib!e rea!
roots for "o!ume The e)treme $oints of intersection re$resent !iquid mo!ar "o!ume and gas mo!ar
"o!ume res$ecti"e!y# re$resented as and in 1ig ID The third# midd!e root# gi"en by $oint
@oA# is a!*ays regarded as un$hysica! and is a!*ays discarded# because it be!ongs to the $ath A/8/
Action Item
for this modu!e
Please note:
date

Problem Set
< 3ubic EOS yie!d three roots for G%factor for a $ure substance at subcritica! conditions Moes that
mean that there is a @GA factor for !iquids7 (sn/t the @GA factor conce$t on!y a$$!icab!e to gases7
6hat does a @G factorA connote for !iquids7

Module Cubic EOS and Their Behavior

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Module Cubic EOS and Their Behavior (II)

(Modified 26 Aug 2008)

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