II / DISTILLATION / Vapour}Liquid Equilibrium: Theory
Adachi Y and Lu BC-Y (1990) Taking advantage of avail-
able cubic equations of state. Canadian Journal of
Chemical Engineering 68: 639}644.
Christiansen LJ and Fredenslund A (1975) Thermodynamic
consistency using orthogonal collocation or composition
of equilibrium vapor compositions at high pressures.
American Institute of Chemical Engineers Journal 21:
49}57.
Derr EL and Deal CH Jr (1969) Analytical solutions of
groups. Correlation of activity coefRcients through
structural group parameters. Proceedings of Interna-
tional Symposium of Distillation 3: 40}51.
Denbigh K (1981) The Principles of Chemical Equilibrium,
4th edn. Cambridge: Cambridge University Press.
Fredenslund A, Gmehling J and Rasmussen P (1977) Va-
pour}Liquid Equilibria Using UNIFAC. Amsterdam:
Elsevier.
Gmehling J, Onken U and Arlt W (1974}1990) Vapour}
Liquid Equilibrium Data Collection; Dechema Chem-
istry Data Series, vol. I, parts 1}8. Frankfurt: Dechema.
Hala E, Pick J, Fried V and Vilim O (1967) Vapour}Liquid
Equilibrium, 2nd edn. Oxford: Pergamon Press.
Hayden JG and O’Connell JP (1975) Generalized method
for predicting second virial coefRcients. Industrial and
Engineering Chemistry. Process Design and Develop-
ment 14: 209}216.
Knapp H, Doring R, Oellrich L, Plocker U and Prausnitz
JM (1982) In: Behrens D and Eckerman R (eds) Chem-
istry Data Series, Vol. VI: VLE for Mixtures of Low
Boiling Substances. Frankfurt: Dechema.
Kojima K and Tochigi T (1979) Prediction of Vapour}
Liquid Equilibria by the ASOG Method. New York:
Elsevier.
Lewis, GN and Randall M (1923) Thermodynamics and
the Free Energy of Chemical Substances. New York:
McGraw-Hill.
Lu BC-Y (1959) Heats of mixing and vapor}liquid equilib-
rium calculations. Canadian Journal of Chemical Engine-
ering 37: 193}199.
Lu BC-Y (1962) Binary vapor}liquid equilibrium data:
Thermodynamic consistency tests. Canadian Journal of
Chemical Engineering 40: 16}24.
Malanowski S and Anderko A (1992) Modelling Phase
Equilibria, Thermodynamic Background and Practical
Tools. New York: John Wiley.
Vapour}Liquid Equilibrium: Theory
A. S. Teja and L. J. Holm, Georgia Institute of
Technology, Atlanta, GA, USA
Copyright ^ 2000 Academic Press
Introduction
The concept of an equilibrium stage in distillation is
based on the assumption that the vapour leaving the
1159
Papadopoulos MN and Derr EL (1959) Group interaction.
II. A test of the group model on binary solutions of
hydrocarbons. Journal of American Chemical Society
81: 2285}2289.
Prausnitz JM, Lichtenthaler RN and de Azevedo EG
(1999) Molecular Thermodynamics of Fluid-Phase
Equilibria, 3rd edn. Englewood Cliffs, NJ: Prentice-
Hall.
Raal JD and Muhlbauer AL (1998) Phase Equilibria,
Measurement and Computation. Washington, DC:
Taylor & Francis.
Redlich O, Derr EL and Pierotti GJ (1959) Group interac-
tion. I. A model for interaction in solutions. Journal of
American Chemical Society 81: 2283}2285.
Reid RC, Prausnitz JM and Poling BE (1987) The Proper-
ties of Gases and Liquids, 4th edn. New York: McGraw-
Hill.
Renon H and Prausnitz JM (1968) Local compositions in
thermodynamic excess functions for liquid mixtures.
American Institute of Chemical Engineers Journal 14:
135}144.
Starling KE (1977) Fluid Properties for Light Petroleum
Systems. Houston, TX: Gulf Publishing Co.
Thomas ER and Eckert CA (1984) Prediction of limiting
activity of coefRcients by a modiRed separation of cohe-
sive energy density model and UNIFAC. Industrial and
Engineering Chemistry. Process Design and Develop-
ment 23: 194}209.
Walas SM (1985) Phase Equilibria in Chemical Engineer-
ing. Boston: Butterworth.
Wilson GM (1964) Vapor}liquid equilibrium. XI. A new
expression for the excess Gibbs energy of mixing. Jour-
nal of American Chemical Society 86: 127}130.
Wilson GM and Deal CH (1962) Activity coefRcients and
molecular structure } activity coefRcients in changing en-
vironments } solutions of groups. Industrial and Engin-
eering Chemistry Fundamentals 1: 20}23.
Won KW and Prausnitz JM (1973) High-pressure vapor}
liquid equilibriums. Calculation of partial pressures
from total pressure data. Thermodynamic consistency.
Industrial and Engineering Chemistry Fundamentals 12:
459}463.
Wong DSH and Sandler SI (1972) A theoretically correct
mixing rule for cubic equations of state. American Insti-
tute of Chemical Engineers Journal 38: 671}680.
stage is in equilibrium with the liquid leaving the
same stage. The use of this concept in the design of
distillation columns requires a description of how the
components of a multicomponent mixture distribute
between the two phases in equilibrium. This description
is provided by phase equilibrium thermodynamics.
The equilibrium relationship for any component
i in an equilibrium stage is deRned in terms of the
1160 II / DISTILLATION / Vapour}Liquid Equilibrium: Theory

distribution coefRcient or K value: relative volatilities) is provided by thermodynamics

yi
Ki"
xj
where yi is the mole fraction of component i in the
vapour phase and xi is the mole fraction of i in the
liquid phase. The more volatile components of a mix-
ture will have higher K values, and vice versa. In
distillation, the efRciency of separation of two com-
ponents is often compared via a quantity called the
relative volatility
ij:
Ki yi/xi

ij" "
Kj yj/xj
A relative volatility close to unity means that the
separation of the two components is likely to be
difRcult, whereas a relative volatility much greater or
much less than unity means that few equilibrium
stages are likely to be needed for separation. For
binary system, eqn [2] can be rearranged to give:
and is discussed below. A more detailed discussion
may be found in textbooks of thermodynamics (see
[1]
Further Reading).
Thermodynamic Framework
Vapour}liquid equlibria (VLE) can be modelled using
the thermodynamic relationship for the equality of
fugacities of a component i in the vapour and liquid
phases. Thus:
fK iL"fK iV (i"1 to m) [4]
[2]
where m is the total number of components in the
system, and L and V represent the liquid phase and
the vapour phase, respectively. In order to use this
relationship, the fugacities must Rrst be related to the
compositions in the two phases in equilibrium. This is
done using the following thermodynamic relationship
in terms of the variables T, P and ni:

  
 
fiK P
V RT

ijxi RT ln " ! dP [5]
yi" [3] ziP ni P
1#(
ij!1)xi 0 T,P,nj

or the equivalent relationship in terms of T, V and ni:

Eqn [3] is plotted in Figure 1 for various (constant)
values of the relative volatility. Note that an increase

  
 
fKi  P RT
in the relative volatility leads to an increase in the RT ln " ! dP
concentration of the more volatile component in the ziP V ni T,V,nj V
vapour phase. When the relative volatility has a value


of 1, yi"xi and separation is no longer feasible. PV
!RT ln [6]
A relative volatility of 1 also signiRes the existence of RT
an azeotrope or a critical point. A framework for the
correlation and prediction of K values (and hence In the above equations, zi is either xi or yi depend-
ing on the phase being considered, and ni is the
number of moles of component i in that phase. The
quantity (fiK /ziP) is called the fugacity coefRcient
K i of
component i in the mixture.

Ideal Systems
In the case of an ideal gas mixture, substitution of the
ideal gas equation PV"nRT into eqn [5] leads to:

fK Vi "yiP [7]
Similarly, substitution of the volume additivity re-
lation for ideal liquid mixtures V"nivLi (where vLi is
the molar volume of component i at the temperature
and pressure of the solution) leads to:

fK Li"xi f Li [8]

where f Li is the fugacity of pure liquid i at the pressure

Figure 1 The y}x behaviour of a binary mixture at constant and temperature of the solution. At constant temper-
temperature for various values of the relative volatility
ij. ature, the effect of pressure on the pure liquid
 II / DISTILLATION / Vapour}Liquid Equilibrium: Theory 1161

fugacity can be obtained from:

v Li
d ln f Li" dP [9]
RT

Integration of eqn [9] from the saturation pressure

to the system pressure leads to:


P
vLi
f Li"f sat
i exp dP [10]
Psat
i
RT

where f sat
i ("
sat sat
i Pi ) is the fugacity of pure i at
saturation,
i is the fugacity coefRcient of pure i at
sat

saturation, and Psat

i is the vapour pressure of pure i.
The liquid molar volume vLi can often be assumed to
be constant with respect to pressure (since liquids are
Figure 2 The P}x}y behaviour at constant temperature of a bi-
incompressible), thus simplifying the exponential nary mixture that obeys Raoult’s law. The dashed line shows the
terms of eqn [10], called the Poynting factor, to: P}x behaviour or the bubble curve. The solid line represents the
P}y behaviour or the dew point curve.

 

i !P)


P
vLi vLi(Psat
exp ! dP +exp [11]
Psat
i
RT RT
only at low pressures ((1 MPa). As a consequence,
At low pressures (P(1 MPa), the Poynting terms K values can be predicted from pure component data
and
sat
i both approach unity and eqn [10] reduces to:
only for such mixtures. The majority of real systems
are nonideal and their thermodynamic description is
f Li"Psat
i [12] discussed below.

Nonideal Systems
Thus, for the simplest case of an ideal gas mixture in
equilibrium with an ideal liquid solution at low pres- Figure 3A, B shows the P}x}y behaviour of systems
sures, eqns [4]}[12] lead to Raoult’s law: that exhibit small negative and positive deviations
from Raoult’s law, whereas Figure 3C and D show
i "yiP
xiPsat [13] systems that exhibit large negative and positive devi-
ations from Raoult’s law, respectively. Large devi-
and, therefore: ations from Raoult’s law often lead to the formation
of minimum pressure (maximum boiling) or max-
yi Psat
i imum pressure (minimum boiling) azeotropes, as
Ki" " [14]
xi P shown in Figure 3C and D. The relative volatility has
and: a value of unity at the azeotropic composition.
Nonideal behaviour depicted in these Rgures can be
Psat
i
described using two approaches } the activity coefRc-

ij" sat [15]
Pj ient approach and the equation of state approach.

The relative volatility of a system that obeys Activity coefVcient approach In this approach, va-
Raoult’s law is thus a ratio of two vapour pressures pour-phase fugacities are written in terms of the va-
and is a function only of the temperature. The pour-phase composition as follows:
yi versus xi behaviour at constant temperature is
therefore as shown in Figure 1, and the P}x}y behav- fK iV"
K ViyiP [17]
iour of such a system is shown in Figure 2. A feature
of this system is that the P}x behaviour (or the bubble where
K Vi is the vapour-phase fugacity coefRcient of
curve) is linear and given by: component i, yi is the mole fraction of i in the vapour
phase and P is the total system pressure. In addition,
i #x1(P1 !P2 )
P"Psat sat sat
[16] liquid-phase fugacities are written in terms of the
liquid-phase composition as follows:
Only a small number of systems containing chemic-
ally similar components obey Raoult’s law, and then fK iL" i x i f i0 [18]
1162 II / DISTILLATION / Vapour}Liquid Equilibrium: Theory

Figure 3 (A) The P}x}y behaviour of a system that exhibits small negative deviations from Raoult’s law. The P}x behaviour of
a system that follows Raoult’s law is shown by the broken line. (B) The P}x}y behaviour of a system that exhibits small postive
deviations from Raoult’s law. Raoult’s law behaviour is shown by the broken line. (C) The P}x}y behaviour of a system that exhibits
significant negative deviations from Raoult’s law leading to the formation of a minimum pressure (maximum boiling) azeotrope. (D) The
P}x}y behaviour of a system that exhibits significant positive deviations from Raoult’s law leading to the formation of a maximum
pressure (minimum boiling) azeotrope.

where i is the activity coefRcient of component i in Hence:

the liquid phase, xi is the mole fraction of i in the
ixiPsat
i "yiP [21]
liquid phase and f 0i is the fugacity of pure liquid i at
the pressure and temperature of the system. Combin- and:
ing eqns [17] and [18], we obtain: Ki"iPsat
i /P [22]
i xi f "
K y P
0
i
V
i i [19] Vapour pressures at subcritical temperatures may
be obtained from experimental data using equations
At low pressures ((1 MPa), eqn [19] can be simpli-
such as the Antoine equation. Activity coefRcients
Red further to yield:
may be obtained from excess Gibbs energy gE models,
i xiPsat
i "
K ViyiP [20] as described below.

as discussed in the previous section. Often

K Vi&1.0 Equation of state approach The equation of state
for vapour phases at moderate pressures. approach uses eqn [17] for the vapour phase and an
 II / DISTILLATION / Vapour}Liquid Equilibrium: Theory 1163

analogous expression for the liquid phase. Thus, for The truncated virial eqn [28] is only applicable to
the liquid phase: gases at densities that are less than about half the
critical density. One of the advantages of the virial
fK Li"
K LixiP [23] equation, however, is that virial coefRcients can be
calculated from intermolecular potential functions.
Substituting these relationships into eqn [4] results
Also, statistical mechanics provides rigorous expres-
in:
sions for the composition dependence of the virial

K Viyi"
K Lixi [24] coefRcients. Thus, the mixture second virial coefRc-
ient is given by:
and:
B" yiyjBij [29]
Ki"
K Li/
K Vi [25] i j

The calculation of K values is therefore reduced where Bii is the second virial coefRcient of component
to the calculation of fugacity coefRcients in the equa- i and Bij is a cross second virial coefRcient. Substitu-
tion of state approach and, at moderate pressures, to tion of eqns [28] and [29] into eqn [5] leads to:
the calculation of activity coefRcients in the activity
coefRcient approach. P
ln
K Vi" [Bii# ykyl(2ki!kl)] [30]
RT 

Calculation of Fugacity where kl"2Bkl!Bkk!Bll. The fugacity coefRcient

Coef\cients of any component in the vapour phase can thus
Calculation of the fugacity coefRcient using eqn [5] or be calculated if the second virial coefRcients of the
eqn [6] requires knowledge of the P}V}T}x behav- pure components and the cross second virial
iour of the system. This information is obtained from coefRcients are available. Since the truncated virial
an equation of state. Two representative types of equation is only applicable to gases at low to moder-
equation of state will be discussed below } a volume- ate pressures, fugacity coefRcients calculated using
explicit virial equation and a pressure-explicit cubic eqn [30] are generally only employed when eqn [20]
equation. A more detailed discussion of types of is used to calculate VLE.
equation of state is available elsewhere (see Further Pressure-explicit Cubic Equation of State
Reading).
Cubic equations of state express the pressure as a cu-
Volume-explicit Virial Equation bic function of the molar volume, and their origin
Virial equations of state are inRnite-series expansions stems from the van der Waals equation, which was
of the compressibility Z as a function either of the the Rrst cubic equation of state to represent qualita-
density or pressure. The pressure series may be writ- tively both vapour and liquid phases. Several hundred
ten as: modiRcation of the van der Waals equation have been
reported in the literature. An example of a recent
PV modiRcation that is better able to represent P}V}T}x
Z" "1#BP#CP2#2 data for both vapour and liquid mixtures is the equa-
RT
tion of state proposed by Patel and Teja in 1982. This
BP (C!B2) 2 equation may be written as:
"1# # P #2 [26]
RT (RT2)
RT a

where B is the second virial coefRcient, C the third P" ! [31]
v!b v2#bv#cv!bc
virial coefRcient, and so on. Typically, the two-terms
truncated form of the virial equation is used for gases where:
at low pressures:
R2T 2c
a"
a [32]
BP Pc
Z"1#BP"1# [27]
RT RTc
b"b [33]
which can be rearranged in the volume-explicit form: Pc

RT RTc
V" #B [28] c"c [34]
P Pc
1164 II / DISTILLATION / Vapour}Liquid Equilibrium: Theory



"[1#m(1!(T/Tc)]2 [35] (2v#b#c)#[4bc#(b#c)]
;ln
(2v#b#c)![4bc#(b#c)]
a"32c#3(1!2c)b#2b#1!3c [36]
2a
(bi#ci)
c"1!3c [37] #
RT ((2v#b#c)![4bc#(b#c)])
c"Pcvc/RTc [38]
a

#
and b is the smallest positive root of: RT[4bc#(b#c)]

3b#(2!3c)2b#32cb!3c"0 [39] ;[ci (3b#c)#bi (3c#b)]



In the above equations, the subscript c denotes (2v#b#c)#[4bc#(b#c)]
a value at the critical point. Note that by setting the ; ln
(2v#b#c)![4bc#(b#c)]
parameter c"0 in eqn [31], the Patel}Teja equation
reduces to the Redlich-Kwong-Soave equation of

2(2v#b#c)[4bc#(b#c)]
state; and by setting c"b, it reduces to the Peng} ! [45]
(2v#b#c)![4bc#(b#c)]
Robinson equation of state. Both the Redlich}
Kwong}Soave and the Peng}Robinson equations are
widely used in process design calculations. For non- Eqn [45] can be used to calculate both the vapour-
polar Suids, c and m are calculated from the follow- and liquid-phase fugacity coefRcients. In the case of
ing relationships in terms of the acentric factor : vapour phase, zi"yi and v is the vapour molar vol-
ume, whereas for the liquid phase, zi"xi and v is the
c"0.329032!0.076799 #0.0211947 2 [40] liquid molar volume. The ratio of the two fugacity
coefRcients yields the K value under the conditions of
m"0.452413#1.30982 !0.295937 2 [41] interest.

A knowledge of Pc, Tc and is therefore sufRcient

to calculated the parameters of the equation of state. Calculation of Activity Coef\cients
Alternatively, c and m may be calculated from ex- Activity coefRcients, i are generally calculated by
perimental values of the vapour pressure and liquid differentiation of the excess Gibbs energy gE:
density of the substance. Several other forms of


eqn [35] suitable for complex molecules have been ngE
RT ln i" [46]
proposed. ni T,P,nj
The parameters a, b and c for a mixture can be
calculated using the following mixing rules: A number of expressions have been proposed for
gE as a function of composition. Some of the more
a
" zizj(a
)ij [42] popular of these are outlined below.
i j

Margules Equation
b" zibi [43]
i The Margules equation is one of the simplest expres-
sions for the molar excess Gibbs energy. For a binary
c" zici [44] solution:
i
gE
where zi can be xi or yi and (a
)ij"(1!kij ((a
)i(a
)j. "x1x2(A21x1#A12x2) [47]
RT
kij is a binary interaction parameter that is usually
obtained by Rtting experimental VLE data. where A12 and A21 are binary parameters dependent
The fugacity coefRcient can be obtained by substi- on temperature, but not on the composition. The
tuting eqns [31]}[44] into eqn [6] leading to: Margules activity coefRcients in a binary mixture are
obtained by differentiation of eqn [47] and are given

  
fK i bi P by:
ln
K i"ln " !ln (v!b)
zi P v!b RT
ln 1"[A12#2(A21!A12)x1]x22 [48]
2 xj
ij aij
!
RT [4bc#(b#c)] ln 2"[A21#2(A12!A21)x2]x21 [49]
 II / DISTILLATION / Vapour}Liquid Equilibrium: Theory 1165

A12 and A21 are generally obtained by Rtting VLE the molar liquid volume vi of the pure component i,
data. Note that the value of the activity coefRcient of and the energies of interaction ij between the molecu-
each component tends to unity as the mole fraction of les i and j as follows:
that component goes to unity. This behaviour is in-

 
herent in all gE models. The Margules equation works vj ij!ii

ij" exp ! [54]
well for binary systems in which the two components vi RT
are very similar in size, shape and chemical nature.
Margules parameters for a large number of systems The expression for the liquid activity coefRcients
are tabulated in DECHEMA books on VLE data. are:
Van Laar Equation ln 1"!ln(x1#
12x2)
The van Laar equation for the excess Gibbs energy



12
21
may be written as: #x2 ! [55]
x1#
12x2 x2#
21x1
gE 2a12x1x2q1q2
" [50] ln 2"!ln(x2#
21x1)
RT x1q1#x2q2



21
12
where q1 and q2 are the effective volumes of the two #x1 ! [56]
molecules and a12 is an interaction parameter. Differ- x2#
21x1 x1#
12x2
entiation according to eqn [46] leads to the following
expressions for the activity coefRcients: The Wilson equation has two parameters
12 and

21 (or equivalently, 12!11 and 21!22) and is
A12 able to correlate VLE data for a wide variety of
ln 1" [51]

 
A12 x1 2 miscible systems, including those containing polar or
1# associating components in nonpolar solvents. How-
A21 x2
ever, the equation is incapable of predicting
A21 liquid}liquid immiscibility in a system.
ln 2" [52]

 
A21 x2 2 For multicomponent mixtures, the Wilson equa-
1# tion is written as follows:
A12 x1

where A12"2q1a12 and A21"q2a12. As in the case of
ik
kj #1! m
the Margules equation, the two parameters A12 and
A21 are obtained by Rtting VLE data. The van Laar
ij
equations have been shown to work well for a num-
ber of binary systems where the size, shape and chem-
ij are required
ical nature of the components are dissimilar, and
parameters for many binary systems have been
tabulated in the DECHEMA data books.
Wilson Equation
The Margules equation is based on the assumption
that the ratio of species 1 to species 2 molecules
surrounding any molecule is the same as the ratio of
the mole fractions of species 1 and 2. A different class
of gE models has been proposed based on the assump-
tion that, around each molecule, there is a
local composition that is different from the bulk com-
position. The Wilson equation is such a local com-
position model and the Wilson excess Gibbs
energy has the following form for a binary system:
gE
"x1 ln(x1#
12x2)!x2 ln(x2#
21x1) [53] energy is:
RT
 
m m
xi
ln k"!ln xj
[57]
j"1 i"1
xj
j"1
Note that only binary parameters
to evaluate activity coefRcients in multicomponent
systems. These parameters are obtained by Rtting
VLE data for the binary pairs, and many of these
parameters have been tabulated in the DECHEMA data
books. Moreover, because a temperature dependence
is included in eqn [54], the same binary parameters
may be used over a range of temperatures (although
no more that about 50 K).
NRTL Equation
The NRTL (non-tandom two-liquid theory) equation
is also based on a local composition model for the
excess Gibbs energy. However, it is applicable to
miscible as well as partially miscible systems due to
the inclusion of a third binary parameter in the
model. The expression for the molar excess Gibbs

 
where
12 and
21 are parameters speciRc to the gE 21G21 12G12
"x1x2 # [58]
binary pair. These parameters are deRned in terms of RT x1#x2G21 x2#x1G12
1166 II / DISTILLATION / Vapour}Liquid Equilibrium: Theory

where ij and Gij are deRned as: gE(combinatorial) 1 2

"x1 ln #x2 ln
RT x1 x2
Gij"exp(!ijij) [59]


z 1 2
gij!gjj # q1x1 ln #q2x2 ln
ij" [60] 2 1 2
RT [65]
gij describes the energy of interaction between com-
gE(residual)
ponent i and j and ij ("ji) is a nonrandomness "!q1x1 ln(1#221)
parameter which is often set equal to 0.3. Thus, only RT
two parameters ij and ji (or, equivalently, gij!gjj !q2x2 ln(2#112) [66]
and gji!gii) are required per binary pair.
The activity coefRcients expressions are as follows: where:
xiri
i" [67]


 
G21 2
12G12 xjrj
ln 1"x 21
2
2 # [61]
x1#G21x2 (x2#G12x1)2 j
xiqi
i" [68]
xjqj

 
G12 2
21G21
ln 2"x 12
2
1 # [62] j
x2#G12x1 (x1#G21x2)2


aji
ji"exp ! [69]
RT
A major advantage of the NRTL equation lies in its
ability to represent highly nonideal systems, par- In eqn [65] z is a coordination number ("10 usu-
ticularly partially miscible systems. ally), i are volume fractions, and i are surface area
For multicomponent mixtures, the liquid-phase ac- fractions for component i. The volume and surface
tivity coefRcients are expressed as: area parameters ri and qi can be evaluated from pure
component molecular structure information and are


m m tabulated in the DECHEMA data books. Thus, there are
jiGjixj m
xrrjGrj two binary parameters aij and aji in the UNIQUAC model
xjGij
ln i"j"1
m
# m
ij!r"1
m and these are found by Rtting binary VLE data. The
Glixl j"1
Gljxl Gljxl activity coefRcient expressions become:
l"1 l"1 l"1



[63] 1 z 1 r1
ln 1"ln # q1 ln # 2 l1! l2
x1 2 1 r2
As with the Wilson equation, only binary data are
needed to calculate activity coefRcients in multicom- !q1 ln(1#221)
ponent systems, and these parameters have been


tabulated in the DECHEMA data books for many sys- 21 12
#2q1 ! [70]
tems. Furthermore, because of the inclusion of the 1#221 2#112
temperature in eqn [60] the parameters obtained by



Rtting VLE data at one temperature may be used to 2 z 2 r2
calculated VLE at other temperatures (within a range ln 2"ln # q2 ln # 1 l2! l1
x2 2 2 r1
of about 50 K).

UNIQUAC Equation !q2 ln(2#112)


The UNIQUAC (universal quasi-chemical theory) equa- 12 21
#1q2 ! [71]
tion expresses the molar excess Gibbs energy as a sum 2#112 1#221
of a combinatorial part and residual part.
where:
gE"gE(combinatorial)#gE(residual) [64]


z
li" (ri!qi)!(ri!1) [72]
The combinatorial part accounts for differences in 2
the size and shape of the molecules, whereas the
residual contribution accounts for energetic interac- The UNIQUAC equation is applicable to a wide range
tions. of systems, including partially miscible systems.
 II / DISTILLATION / Vapour}Liquid Equilibrium: Theory 1167

For multicomponent systems, the UNIQUAC equation XmQm

m" [83]
becomes:
XnQn
i z i i m n
ln i"ln # qi ln #li! xjlj


xi 2 i xi j"1 amn
mn"exp ! [84]
T


m m
jij
!qi ln jji #qi!qi [73]
m xivmi
j"1 j"1
kkj
Xm" i
[85]

j"1
Once again, only pure component and binary
data are needed to calculate the parameters. UNIQUAC
parameters for over 6000 binary systems have been
tabulated in the DECHEMA data series on VLE.
UNIFAC Group Contribution Method
When values of Margules, van Laar, Wilson, NRTL
or UNIQUAC parameters are not available in the litera-
ture, or when no VLE data for the system of interest
have been measured, the UNIFAC (UNIQUAC functional
group activity coefRcients) method may be used to
estimate activity coefRcients. The UNIFAC method is
a group contribution technique for the estimation of
the parameters amn of the excess Gibbs energy model.
The method expresses the molar excess Gibbs energy
as a sum of a combinatorial part and a residual part
and uses the same combinatorial part as the UNIQUAC
equation. In terms of the activity coefRcient:
ln i"ln Ci#ln Ri
12"!449.3 and
21"!835.9 reported


xi vki
i k
Since the group volume parameters Rk and the
group area parameters Qk are known, the only un-
knowns in the UNIFAC equations are the group interac-
tion parameters amn and anm. These have been
tabulated for a large number of groups. Moreover,
updated parameters are published regularly in the
literature. The UNIFAC method has been successfully
applied to a wide variety of binary and multicompo-
nent systems.
Examples of Use
Subcritical Vapour+Liquid Equilibria
Figure 4 shows the P}x}y behaviour of the meth-
anol}water system at 313 K calculated using the
activity coefRcient approach. Activity coefRcients
were obtained from the Wilson equation using para-
[74]
meters
in DECHEMA data books. Fugacity coefRcients in the



i z i ri
ln Ci"ln # qi ln # i li! lj [75] vapour phase were assumed to be equal to 1.0. Note
xi 2 i rj that the Wilson parameters were obtained by Rtting
the data, and therefore reproduce the experimental
ri" vkiRk [76]
k

qi" vkiQk [77]

k

The group Rk, and the group area Qk have been

tabulated for a large number of groups. vki is the
number of groups of k kind in molecule i.
The residual contribution is expressed as follows:

ln Ri" Qk(ln k!ln (i)

k ) [78]
k

ln k"Qk(1!ln Ek!Fk) [79]

ln (k)
k "Qk (1!ln Ek !F k )
(i) (i) (i)
[80]

Ek"11k#22k#33k#2 [81]

1k1 2k2 3k3

Fk" # # #2 [82] Figure 4 The P}x}y behaviour of methanol}water at 313 K
E1 E2 E3 correlated with the Wilson equation.
1168 II / DISTILLATION / Vapour}Liquid Equilibrium: Theory

Figure 5 The P}x}y behaviour of methanol}water at 373 K

predicted using Wilson equation constants obtained at 313 K.
Figure 7 The P}x}y behaviour of methanol}water at 373 K
predicted with Patel}Teja equation using binary parameters ob-
tained at 313 K.
data (open circles) reasonably well in this system.
Figure 5 shows that when the same parameters are
used to calculate VLE data for methanol}water at 373 K using the same values of the kij parameters, as
373 K, good agreement is obtained with experimental shown in Figure 7.
data.
Figure 6 shows the P}x}y behaviour at 313 K of
Supercritical Vapour+Liquid Equilibria
the same system correlated using the Patel}Teja equa-
tion of state. Two kij values were required to correlate Figure 8 shows the P}x}y behaviour of the carbon
the data (k12"!0.0923 and k21"0.0748) and, in dioxide}propane system at 328 K predicted using the
general, excellent agreement was obtained between equation of state approach with the Patel-Teja
calculated and experimental values. Moreover, the equation of state. The two binary interaction
equation of state was successful in predicting data at

Figure 8 The P}x}y behaviour of CO2}propane mixtures at

Figure 6 The P}x}y behaviour of methanol}water at 313 K 328 K predicted using the Patel}Teja equation of state with binary
correlated with the Patel}Teja equation. parameters obtained from data at 244 K.
 II / ELECTROPHORESIS / Agarose Gels 1169

See also: II/Distillation: Historical Development; Model-

ling and Simulation; Multicomponent Distillation; Theory of
Distillation; Vapour-Liquid Equilibrium: Correlation and
Prediction.

Further Reading
Dymond JH and Smith EB (1980). The Virial CoefTcients
of Pure Gases and Mixtures: A Critical Compilation.
New York: Oxford University Press.
Fredenslund A, Gmehling J and Rasmussen P (1977) Va-
pour}liquid Equilibria Using UNIFAC } A Group
Contribution Method. New York: Elsevier Science.
Ghemling J, Onken U and Arlt W (eds) (1978) Vapour}
liquid Equilibrium Data Collection. Frankfurt: DE-
CHEMA.
Hansen HK, Rasmussen P and Fredenslun A et al. (1991)
Vapour}liquid equilibrium by UNIFAC group contribu-
tion. 5. Revision and extension. Industrial & Engineer-
ing Chemistry Research 30: 2352}2355.
Figure 9 The P}x}y behaviour of methane-n-butane mixtures Knapp H, Reichl A and Sandler SI (1998) Analysis of
at 344 K predicted using the Patel}Teja equation of state with
thermodynamic model equations: mixing rules in cubic
binary parameters obtained from data at 186 K.
equations of state. Industrial & Engineering Chemistry
Research 37: 2908}2916.
parameters (k12"0.143 and k21"0.121) were ob- Patel NC (1996) Improvements of the Patel}Teja equation
tained by Rtting data at a much lower temperature of of state. International Journal of Thermophysics 17:
244 K. The predictions are in excellent agreement 673}682.
with experiment, even though the extrapolation is to Patel NC and Teja AS (1982) A new cubic equation of state
a temperature that is above the critical temperature of for Suids and Suids mixtures. Chemical Engineering
carbon dioxide (304 K). A similar extrapolation using Science 37: 463}473.
the Patel}Teja equation of state is shown in Figure 9 Prausnitz JM, Lichtenthaler RN and Gomes de Azevedo
where VLE in the methane-n-butane system at 344 K E (1999) Molecular Thermodynamics of Fluid-phase
Equilibria, 3rd edn. Englewood Cliffs: Prentice
have been predicted using binary parameters (k12"
Hall.
0.021 and k21"0.002) obtained at 186 K. Note that Reid RC, Prausnitz JM and Poling B (1987) The Properties
the extrapolation is carried out to a temperature that of Gases and Liquids, 4th edn. New York: McGraw-
is well above the critical temperature of methane Hill.
(190 K). Finally, it should be added that the activity Smith JM, Abbott MM and Van Ness HC (1996) Introduc-
coefRcient approach described above cannot be used tion to Chemical Engineering Thermodynamics, 5th
to correlate or predict supercritical VLE behaviour. edn. New York: McGraw-Hill.

ELECTROPHORESIS

following Araki’s preparation of it in 1937 as an

Agarose Gels
J. R. Shainoff, Cleveland State University,
Cleveland, Ohio, USA
Copyright ^ 2000 Academic Press
Development
Agarose is a uniquely nonadhesive hydrocolloid that
has found many uses in the separation sciences
apparently sulfate-free component distinct from the
sulfate-rich agaropectin in agar. Agar and many of
the other hydrocolloids derived from certain species
of seaweed had been used mainly in food preparation
dating back to the seventeenth century in Japan. Agar
was introduced as a medium for immunoelectrophor-
esis by Grabar and Williams in 1953, and the original
technique is occasionally used today. Citrated agar
electrophoresis is the current principal method
for identiRcation of haemoglobin variants. Agar was