Chemical Engineering 301

Lecture Notes
Chapters 10-12. Phase Equilibrium and Solutions
apor-Liquid Phase Equilibrium at Lo! Pressures " #aoult$s La!
Consider a system with two phases (vapor and liquid) at given values of pressure
and temperature.
P
T
V
L
What we want to know is the equilirium relationship etween the measurale
variales P! T! y
i
! x
i
in this system.
The simplest relationship is "aoult#s law! whi$h is ased on assumptions of ideal
gas for the vapor phase and ideal liquid solution for the liquid phase%
i
sat
i i
x P Py
Calculations %sing #aoult&s La!
'ubble-point pressure prolem && T!x given && P!y unknown.
This is a straight&forward $al$ulation. The vapor pressures are found at the
given temperature! whi$h allows dire$t $al$ulation of the pressure and
vapor mole fra$tions%

Py P P x
y
P x
P
i i
sat
i
i
i
sat
i
'ubble-point temperature prolem && P!x given && T!y unknown.
' trial and error pro$edure must e followed! where T is assumed! the
vapor pressures $al$ulated! and then see if the $orre$t total pressure is
otained (or the vapor mole fra$tions sum to unity).
y
P x
P
i
i
sat
i

(
(e!-point pressure prolem && T!y given && P!x unknown.
)o trial and error is needed! as P $an e dire$tly $al$ulated.
( )
x
Py
P
x
P
y P
i
i
i
sat
i
i i
sat

(
(
*
(e!-point temperature prolem && P!y given && T!x unknown.
+uess a T! find the vapor pressures! and see if the liquid mole fra$tions sum
to unity.
x
Py
P
i
i
i
sat

(
,is$uss $al$ulation of a y&x diagram for this system at fi-ed P.
)-*alues+ ,lash calculations+ and relati*e *olatilities
,is$uss the T&x&y diagram (.ig. (/.(0! p. 123). 4t represents all possile
dew and ule points for this system at the pressure given.
,is$uss the P&x&y diagram (.ig. (/.((! p. 122). 4t represents all possile
ule and dew points for this system at the T given.
' vapor&liquid equilirium ratio (K&value) is defined for a $omponent as
the ratio of mole fra$tion in the vapor to mole fra$tion in the liquid for that
$omponent.
The $riteria for flash $al$ulations $an e written if various forms. ' useful
one is given elow.
( )
K
y
x
P
P
f P T
z K
V K
i
i
i
i
sat
i i
i

( ! )
( )
(
( (
/
T! P! and feed $ompositions (z
i
#s) are know. ' trial and error for V must
e done (fra$tion to vapor stream). 5ee 5e$. (/.3 for the derivation.
'$$ording to "aoult#s law! the relative volatility (defined elow) is 6ust the
ratio of $omponent vapor pressures.
"elative volatility%

ij
i i
j j
i
j
i
sat
j
sat
y x
y x
K
K
P
P

*
*
-odi,ied #aoult$s La! - Lo! Pressures
't low pressure! where gases $an e $onsidered ideal! it may e ne$essary
to $orre$t for liquid&phase nonidealities! using a 78odified "aoult#s Law9
( ) s x P T f
P
P
x
y
K
x P Py
i
i
sat
i
i
i
i
i i
sat
i i
: ! !

5ee pp. 12;&<2 for $al$ulations of various phase equilirium prolems.

'$tivity $oeffi$ients $ome from e-perimental data (using empiri$al
equations)! or from estimation te$hniques! su$h as the =)4.'C method
presented in 'ppend. >.
.igh Pressures - )-alues ,or Light ./drocarbon S/stems
,is$uss P&T diagrams for mi-tures && refer to .ig. (/.<! p. 113.
.or any given mi-ture! there is a unique ule&point $urve and a unique dew&
point $urve! $onne$ted at the $riti$al point.
"etrograde $ondensation $an o$$ur for some systems! parti$ularly petroleum gases
$ontaining heavy hydro$arons! found as single&phase fluids in deep reservoirs at
high pressure and temperature (gas $ondensate fluids). 4f the pressure is redu$ed
at $onstant temperature! it is possile to hit the dew&point $urve! resulting in liquid
drop&out or 7retrograde $ondensation9.
The ethane&heptane system is a simple demonstration of this. )ote that retrograde
$ondensation $an o$$ur for an ??.@ mol A ethane mi-ture! ut not for a 03.< mol
A ethane mi-ture.
,ePriester Charts for estimation of K&values.
The assumption of ideal gas for the vapor phase restri$ts the use of
"aoult#s law to low pressures. 4f instead! the vapor phase is assumed to
form an ideal solution! then the vapor&liquid equilirium relations $an e
written in terms of K&values! as indi$ated elow%
( ) T P K K
i i
!
This is the asis for the ,ePriester Charts (pp. 1<3&@).
Bule&point $al$ulations%
y K x
i i i
(
,ew&point $al$ulations%
x y K
i i i
( *
Both require trial and error for the unknown T or P.
C-ample Prolem% Cstimate the vapor pressure $urves and the dew& and
ule&point $urves for the ethane D n&heptane system (<?.@ mole A
ethane). Compare with .ig. (/.<! p. 113.
0he 1eneral Nature o, Phase Equilibria
Phase equiliria $ategories%
Positive deviations from "aoult:s law E due to nonideal solution ehavior E
unlike mole$ules do not have the same attra$tions as like mole$ules E P&x
$urve lies aove straight line etween vapor pressures.
)egative deviations from "aoult:s law E due to nonideal solution ehavior
E unlike mole$ules attra$t ea$h other strongly $ompared to like mole$ules
(maye form a weak $omple-) E P&x $urve lies elow straight line etween
vapor pressures.
.
4f deviations e$ome large enough! aFeotropi$ ehavior $an o$$ur.
,is$uss .igs. (/.?&;! pp. 11;&2/.
4f positive deviations e$ome large enough! partial mis$iility $an o$$ur
(i.e.! liquid reaks into two separate phases).
,is$uss .igs. (2.(3&(?! pp. <@/&(.
1eneral Phase Equilibrium #elations
Phase equilirium variales% T! P! moles of ea$h $omponent
Consider a $losed system with no $hemi$al rea$tions. The fundamental property
relation with T and P as independent variales involves the +is free energy%
dG V dP S dT
V
G
P
S
G
T
t t t
t
t
T
t
t
P

_
,

_
,

)ote that only the (st and 0nd laws are involved in deriving this property relation!
plus the definition of G (G G H&TS).
4f the system $an e-$hange mass with its surroundings (another phase)! then it
e$omes an open system. The fundamental property relationship must e
modified! e$ause the total +is free energy will depend on the amount of ea$h
sustan$e present in the system (phase of interest). Thus! the numer of moles of
ea$h $omponent e$ome independent variales! in addition to P and T%
dG V dP S dT dn
G
n
nG
n
t t t
i
i
N
i
i
t
i
T P n s
i
T P n s
j j
+

_
,

_
,

(
! ! : ! ! :
This new defined property is $alled the $hemi$al potential for $omponent i in a
mi-ture.
't equilirium! the temperature and pressure must e the same in all phases! for
thermal and me$hani$al equilirium $onsiderations (i.e.! no driving for$es to $ause
flu-es of heat or fluid movement).
Consider a system $ontaining two phases (vapor and liquid! V and L) at
temperature T and pressure P. Ca$h phase is an open system! e$ause it $an
e-$hange energy and mass with the other phase. The entire system is $onsidered
to e isolated from the surroundings.
4n the vapor and liquid phases we $an write the following fundamental property
relations
( ) ( ) ( )
( ) ( ) ( )
d G V dP S dT dn
d G V dP S dT dn
t
V
t
V
t
V
i
V
i
V
t
L
t
L
t
L
i
L
i
L
+
+

We $an add these to get the total $hange in +is free energy for the entire system
dG V dP S dT dn dn
t t t
i
V
i
V
i
L
i
L
+ +


But! sin$e this is a $losed system! the last two terms must sum to Fero. 'lso! any
mass leaving one phase must enter the other.
( )


i
V
i
V
i
L
i
L
i
V
i
L
i
V
i
L
i
V
dn dn
dn dn
dn

+


/
/
5in$e the dn:s are aritrary independent variales! we $on$lude that

i
V
i
L
i N ( 0 1 ! ! !....!
This $an e e-panded to any numer of phases.
Thus! in addition to thermal and me$hani$al equilirium! the $hemi$al potential for
any given $omponent must e the same in all phases at equilirium.
This is phase equilirium (i.e.! no driving for$es for diffusion).
't equilirium in a system of phases and ) $omponents!


i i i
i N .... ! !....! (0
Thus! we have derived the phase equilirium relations without any new $on$epts
eing introdu$ed! in addition to the (st and 0nd laws.
2ugacities
Hur prolem with $hemi$al potentials is that we have no real feelings aout how
they ehave.
Thus! it is traditional to throw them away! in favor of another defined property!
fuga$ity.

i i
o i
i
o
i i
RT
f
f
f Py as P


ln

/
The hat over the symol for fuga$ity means for a $omponent (i) in a mi-ture. .or
pure fluids! the hat is left off. 4n this e-pression! oth $hemi$al potentials are at
the same temperature (T)! thus! so are the fuga$ities. The supers$ript 7o9 means in
some aritrarily defined standard state.
.or an ideal gas mi-ture! fuga$ity is equal to partial pressure. This is at least some
progressI We know aout ideal gases! and oth P and y
i
are measurale
properties.
4n terms of fuga$ities! the phase equilirium relations do not $hange%

......

! !.... ! f f f i N
i i i

( 0
0hermod/namic Properties o, -i3tures
4deal gas mi3tures
P Py
H y H
S y S R y y
G y G RT y y
i
i i
i i i i
i i i i

ln
ln
4deal solutions
i i i
i i i
i i i i
i i i i
i i
i i
x f f
x RT G
x x RT G x G
x x R S x S
H x H
V x V

+
+

J
ln
ln
ln

Thus! ideal solutions e-hiit no volume $hange on mi-ing and no heat of

mi-ing.
#ead Liquid -i3tures && Partial 8olar and C-$ess Properties
Partial molar properties are defined y
M
nM
n
i
i
T P n
j

_
,

! !
Thus! the partial molar +is free energy is the $hemi$al potential%

i
i
T P n
i
nG
n
G
j

_
,

! !
E3cess properties are defined y
M M M
E id

where the ideal solution value is at the same T ! P! and $omposition as the
a$tual mi-ture.
Thus! the volume and enthalpy of a real mi-ture $an e $al$ulated from the
e-$ess volume and e-$ess enthalpy y the following%
E
i i
E id
E
i i
E id
H H x H H H
V V x V V V
+ +
+ +

Cnthalpies of real liquid mi-tures are also represented y data on heats of

solution! or graphi$ally on H&x diagrams (see 5e$. (0.2! p. 220).
2ugacities in -i3tures - 4deal 'eha*ior
+as Phase && 4deal +ases

f Py
i
V
i

Liquid Phase && 4deal 5olutions

f f x
i
L
i
L
i

The $oeffi$ient on the ">5 is the fuga$ity of the pure liquid at the same
T and P as the a$tual liquid mi-ture.
Below! we will find that it is $losely appro-imated y the vapor pressure of
$omponent i at temperature T.
The aove relation is $alled the Le!is5#andall rule (see p. 2/( in te-t).
2ugacities in -i3tures - #eal 1as and Liquid 'eha*ior
+as phase fuga$ity $oeffi$ients

f Py
as P
i
V
i i
V
i
V

( /
( )
ln

! !

i
i
P
P T n
n Z
n
dP
P
j

_
,

(
/
Liquid phase a$tivity $oeffi$ients

f f x
i
L
i
L
i i

f P
V P P
RT
i
L
i
sat
i
sat i
L
i
sat

1
]
1
e-p
( )
>enry:s law approa$h for dilute $omponents
The a$tivity $oeffi$ient $an e very large near infinite dilution for a
$omponent (f&- slope quite different).

f k x
k f
i
L
i i
i i
L
i

This $an e taken as the ideal dilute solution (>enry:s law)! and $orre$ted
with a different a$tivity $oeffi$ient%
( )
( )

f k x HL
HL
i
L
i i i
i
i
i

The liquid&phase a$tivity $oeffi$ients $an e related to the e-$ess +is

free energy

i i
id
i i
id i
L
i
L
i
i
i
E
i
G G RT
f
f x
RT
G RT


ln

ln
ln
4t $an also e shown that the following hold
G RT x
x d at const T P
E
i i
i i

ln
ln . !

/
The first of these equations is used to $al$ulate e-$ess +is energies from
VLC data.

The latter is used to test VLC data for thermodynami$ $onsisten$y.
2ugacities in Liquid -i3tures - Empirical #elations
Cmpiri$al equations are often used to fit e-$ess +is free energy as a fun$tion of
$omposition.
8argules%
[ ]
( ) [ ]
( ) [ ]
G
RT
x x A x A x
x A A A x
x A A A x
E
+
+
+
( 0 0( ( (0 0
( 0
0
(0 0( (0 (
0 (
0
0( (0 0( 0
0
0
ln
ln

)ote that the $onstants are equal to the limiting values of the logrithms of the
a$tivity $oeffi$ients for the 8argules equations.
"edli$h&Kister%
( )
[ ]
G
RT
x x A B x x
E
+

( 0 ( 0
( 0
ln ln L L
)ote that the "edli$h&Kister equation is identi$al to the two&suffi- 8argules
equations given aove%
( ) ( )
( ) ( )
G
RTx x
A x x B x x
A B x A B x
A A B
A A B
E
( 0
( 0 ( 0
( 0
0(
(0
+ +
+ +
+

MMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMM
,is$uss the VLC data for 8CK(()DToluene(0) && Tale (0.(! .igs. (0.0&1!
pp. 2(@&?. ,raw a pi$ture of the system. This system e-hiits positive deviations
from "aoult:s law.
Class e-er$ise% ,etermine A
(0
and A
0(
from these data.
Class e-er$ise% ,erive the a$tivity $oeffi$ient e-pressions for these data.
,is$uss the VLC data for Chloroform(()D(!2&dio-ane(0) && Tale (0.1! .igs. (0.3!
pp. 20<&3. This system e-hiits negative deviations from "aoult:s law.
Class e-er$ise% ,etermine A and B from these data.
MMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMM
Phase Equilibrium - #aoult&s La!
Consider two phases! vapor and liquid! where the gas phase is an ideal gas
mi-ture! and the liquid phase is an ideal liquid solution.
The phase equilirium relations e$ome

! ! .... ! f f i N
Py f x
i
V
i
L
i i
L
i

( 0
'ssume that the effe$t of pressure is negligile on the pure liquid fuga$ity! so that
it $an e evaluated at the vapor pressure for $omponent i rather than at P.
( ) ( )
f P T f P T
i
L
i
L
i
sat
! !
5in$e we are assuming that the gas phase ehaves like an ideal gas! and sin$e the
mole fra$tion of $omponent i is unity
( ) ( )
f P T f P T P
i
L
i
sat
i
V
i
sat
i
sat
! !
5ustituting this aove! gives "aoult#s law%
Py P x
i i
sat
i

4f the assumption of ideal liquid solutions is rela-ed! ut all other assumptions

remain! then the 8odified "aoult#s law is otained%
i i
sat
i i
x P Py
'asis ,or (ePriester Charts ,or Light ./drocarbons
4n general! the e-pressions for K&values are
( )
( )
K
y
x
P
P
V P P
RT
K K P T y x
i
i
i
i
sat
i
sat
i
i
V
i
L
i
sat
i i

1
]
1
1

e-p
! ! !
'ssume ideal solutions in oth phases
( )
( )
K
y
x
P
P
V P P
RT
K K P T
i
i
i
i
sat
i
sat
i
V
i
L
i
sat
i i

1
]
1
1

e-p
!
This is the asis for the ,ePriester Charts (pp. 1<3&@).
Equations o, State ,or )-*alues
4n modern pra$ti$e! VLC $al$ulations for light&hydro$aron systems are done
using $omputer $al$ulations ased on equations of state! su$h as the 5oave&
"edli$h&Kwong (5"K) equation or the Peng&"oinson (P") equation.
4n this approa$h! fuga$ity $oeffi$ients are used to e-press the fuga$ity of oth the
liquid and vapor phases relative to the ideal gas.
The following phase equilirium relations result%
Py Px
K
i i
V
i i
L
i
i
L
i
V

The same equation of state is used to evaluate the two fuga$ity $oeffi$ients! whi$h
are fun$tions of (T! P! x
i
#s) and (T! P! y
i
#s)! respe$tively.