r~UTTERWQRTH hit J. RejHg. Vol. 18, No. 8, pp.

550 556, 1995

~E I N E M A N N Copyright :~('~1995 Elsevier Science Ltd and I1R
Printed in Great Britain. All rights reserved
0140-7007/95/$10.00 + .00

A method for the prediction of vapour-liquid equilibria of refrigerant

mixtures at low and moderate pressure
M. Barolo*
Istituto per la Tecnica del F r e d d o , C . N . R . , C o r s o Stati Uniti, 4, 1-35020 P a d o v a P D , Italy

A. B e r t u c c o
I s t i t u t o di I m p i a n t i Chimici, Universit& di P a d o v a , via M a r z o l o , 9, 1-35131 P a d o v a P D ,
Italy

G. S c a l a b r i n
I s t i t u t o di Fisica T e c n i c a , Universitfi di P a d o v a , via Venezia, 1, 1-35131 P a d o v a P D ,
Italy
Received 22 February 1995; revised 15 June 1995

This paper is a contribution to the development of a method for the prediction of the thermodynamic
behaviour of refrigerant mixtures at low and moderate pressure, for which experimental data are not always
available. The proposed model is based on a modified Redlich-Kwong-Soave equation of state, with
mixing rules as proposed by Huron and Vidal. The calculation of the attractive parameter is based on
infinite-pressure activity coefficients according to Soave et al. Activity coefficients are expressed by a group-
contribution model derived from UNIFAC. A list of groups and subgroups is proposed for CFCs, HCFCs,
HFCs and FCs. Two interaction parameters are regressed from experimental infinite-dilution activity
coefficients of binary mixtures. As a result, only the structure, critical constants and vapour pressure of pure
components are needed to calculate thermodynamic properties of refrigerant mixtures. The proposed
approach is able to predict experimental data with satisfactory accuracy over the full composition range.
(Keywords: refrigerant mixtures; vapour-liquid equilibria; group contribution; prediction; equation of state)

M6thode de pr6vision de l'6quilibre vapeur-liquide des m61anges

frigorifiques 5. des pressions faibles et mod6r6es
Ce rapport vise it contribuer it la raise au point d'une m~thode permettant de pr~voir le comportement
thermodynamique des m~langes de frigorigbnes it des pressions faibles et mod~rOds. Le modble proposd se fonde
sur une ~quation d'dtat Redlieh-Kwong-Soave modifi~e, avec les rbgles de mdlanges propos~es par Huron et
Vidal. Le calcul du parambtre intdressant s'effectue avec les coefficients d'activitd it pression infinie de Soave et
al. Les coefficients d'aetivitk s'exprime clans un modkle dlabord it base des contributions des groupes de mOlanges
et d&ivd de eelui de I'UNIFAC. On propose une liste de groupes et de sous-groupes pour les CFC, les HCFC, les
HFC et les FC. On trouve, par rdgression it partir des coefficients d'activitO appliquOs it des solutions infiniment
dilud de rndlanges binaires, deux parambtres d'interaetion. Par consequent, seul la structure, les constants
critiques et la pression de vapeur des composants purs, sont ndcessaires au calcul des propriOt&
thermodynamique des m~langes de frigorigenes. La d&narche proposde permet de pr~voir, de manibre
suffisamment precise, des donn~es exp&imentales, sur l'ensemble de la gamme des compositions.
(Mots cl6s: fluide frigorig6ne; 6quilibre vapeur-liquide; contribution du groupe, pr+vision; 6quation d'&at)

The search for alternatives to substitute the chlorofluor-
ocarbons as refrigerants is mainly devoted to mixtures,
of both azeotropic and non-azeotropic type. However,
the number of mixtures of potential interest for use as
working fluids is very large. As it is too expensive to
measure directly the thermodynamic properties of all of
these alternatives, a first screening could be done by
* Present address: Istituto di Impianti Chimici, Universit~ di Padova,
via Marzolo, 9, 1-35131 Padova PD, Italy
means of a model able to correlate and predict their
behaviour with reasonable accuracy; then the actual
measurement of mixture properties would be carried out
on a smaller list of candidates only.
The aim of this study is to develop and test a predictive
method for the calculation of vapour-liquid equilibria
(VLE) of mixtures of CFCs, HCFCs, H F C s and FCs.
Classical models based on a group-contribution concept
and an excess Gibbs free-energy approach, such as
U N I F A C 1, are not suitable to the scope, as they can be

550
 Prediction of v&pour-liquid equilibria of refrigerant mixtures 551

Nomenclature
a Attractive parameter of the EOS Greek letters
art,m Interaction coefficient ct Temperature dependence function of
A Reduced attractive parameter of the EOS parameter a
b Repulsive parameter of the EOS 7 Component activity coefficient
bn,g¢l Interaction coefficient F Group activity coefficient
B Reduced repulsive parameter of the EOS O Group surface area fraction
BV Second virial coefficient u Number of groups
G Gibbs free energy q~ Fugacity coefficient
H Enthalpy Correction factor in Equation (15)
kij Binary interaction coefficient Interaction parameter
Ki Equilibrium ratio Superscripts
nc Number of components oe Infinite pressure reference state
np Number of experimental data points E Excess property
P Pressure L Liquid phase
pvap
Vapour pressure R Residual part of UNIFAC activity
Q Group surface area coefficient
R Universal gas constant V Vapour phase
T Temperature Subscripts
U Molar volume c Critical condition
X Mole fraction in the liquid phase i,j Component indices
X Group mole fraction i(j) Component i infinitely diluted i n j
Y Mole fraction in the vapour phase k, m, n Group indices
Z Mole fraction (generic) r Reduced property
Z Compressibility factor

applied successfully only at low pressure, while there is
a need to work up to 3-4 MPa; on the other hand,
even the most recent modifications of UNIFAC 2'3 do
not contain all the subgroups necessary to represent the
compounds of interest in refrigeration. An example of
the use of UNIFAC to calculate excess properties
of absorption refrigeration mixtures is reported by
Borde4.
In our opinion, however, it is convenient to apply an
equation of state (EOS), as many authors have proposed
in these last years. Traditionally, cubic EOSs with
classical mixing rules are mostly used; a review in this
area is
• given, for example, by Gow 5. In other cases, non-
cubic EOSs have been proposed 6'7, but all of these
methods require the knowledge of empirical mixing rules
with interaction parameters kq, which are calibrated on
binary data and are often of a non-predictable nature.
Sometimes, as done by Fransson et al. 8, a temperature
dependence of kij is considered to reproduce experi-
mental data better. However, as outlined by Morrison
and McLinden7, in order to represent binary VLE data
properly the kij should also have a composition
dependency. With these limitations, such models are
useful for data reduction purposes, but cannot be applied
as predictive tools because, when the kq are set to zero,
large errors arise in the calculation of mixture properties,
such as VLE, PVTx, and H E (see for example the work
by Bertucco et al.9).
A predictive method has already been proposed by
Fransson et a/. l°, who developed a group-contribution
EOS based on the Abdoul-Rauzy-P+neloux method ll
previously derived for hydrocarbons. In this case, as for
UNIFAC, the mixture properties are calculated as a
combination of properties of functional groups, which
are contained in the components involved, but the frame
of the model is an EOS, which is profitably applicable
not only at low pressure.
Recently, several models involving cubic EOSs com-
bined with the UNIFAC excess free-energy expression
have also been proposed for the prediction of VLE; a
work by Voutsas et al. 12 reviews a number of them.
However, it has to be noted that, so far, they have not
been applied to refrigerant mixtures•
In our work the Redlich-Kwong-Soave (RKS) cubic
EOS 13 is used with non-classical mixing rules for
parameter a; this is related to the value of the excess
Gibbs free energy1at infinite pressure (as suggested by
Huron and Vidal 4), which is in turn expressed by a
UNIFAC-type group-contribution model. Following a
procedure recently devised • 15 • -
, lnfimte-dilution 1
activty
coefficients were selected as data source for parameter
calculation. This was done essentially for two reasons:
their experimental determination is relatively easy; and
interpolation from infinite dilution towards the middle
composition range generally yields acceptable values of
the activity coefficients, while the reverse may not be true.
The scope of the work is to test the ability of the
proposed model to predict the VLE of binary mixtures
including CFCs, HCFCs, HFCs and FCs over the full
composition range at low and moderate pressure.
The model
Equation o f state
The Redlich-Kwong cubic EOS as modified by Soave 13
is considered
RT a
P - (1)
v - b v ( v + b)
552 M. Barolo et al.

where P, T and v are pressure, temperature and molar activity coefficients at infinite pressure (superscript oc):
volume of the mixture; R is the universal gas constant;
and a, b are the mixture parameters. By defining the In 7~ = In 7i°oR = Z tyk,i( In Fk -- In Fk,i) (8)
dimensionless variables k

aP bP
A R2T2, B = RT' In r k = Qk 1 - In (~mff)m,k --
A a Pv ) ~ (gn~n,,,
n
= bRr; Z = RT (2)
(9)
Equation (1) can be rewritten as
with
Z3 Z2 ÷ Z.B(A_B -1- B ) - - ~A B z = O (3) XmQm (10)
For pure and subcritical components, A and B are
Om -- ZXnQ"
n
functions of P, T, critical pressure Pc, critical tempera-
ture Tc, and vapour pressure pvap: y ~ Um,jZj
Pr J (11)
A = 0.427 484(P yap) ~ (4a)
j n
B = 0.086 64 Pr (4b)
Vr where Umd is the number of groups of type m in
component j, and %,m is defined by
In Equations (4a) and (4b), a is a generalized function of
pvap as reported by Soave 16, and subscript r indicates
reduced properties. Mixture parameters are derived from
~)n,m = exp(-an'm +~ n'm/T) (12)
pure component ones A i and Bi by means of combina-
tion and mixing rules. According to Huron and Vida114 Note that, with respect to original UNIFAC 1, neglecting
the combinatorial part means that only group surface
B= E ziBi (5) areas Qk are needed. Moreover, the temperature
i
dependence of the interaction parameters ~,,m (Equation
A ~i (Ai ln"/~.'~ (12)) has been improved, in order to take into account
-~= zi -ffi ln2 J (6) also polar effects. Finally, according to Equation (12),
where zi is the mole fraction of component i (in either the either symmetrical or asymmetrical parameters can be
liquid or vapour phase), and "y~ is its activity coefficient used.
in the mixture, which is evaluated in the reference state at As not all the values of Qk were available from
infinite pressure. UNIFAC, they were calculated from Bondi 17, and are
Thus the fugacity coefficient of component i in the listed in Table 1.
mixture at the system temperature and pressure is
expressed by Parameter determination
ln~i = ~ 2 ( Z - 1 ) - I n ( Z - B ) A complete table including all functional groups of
interest for refrigeration applications is beyond the scope
of this work; in order to verify the proposed procedure
(~ lnT~.~ln2
J ln(1 + ! ) (7) and show the potential of the method, only two main
groups and ten subgroups have been considered, as
reported in Table 1. More details on group subdivision
Group contributions are presented in the section 'Results'.
A simplified UNIFAC model, reduced to the residual According to Soave et al. 15, in order to determine the
part (superscript R), is proposed to reproduce the interaction parameters it is useful to refer to infinite-
dilution activity coefficients of component i in j, % (j). If
Table 1 List of main groups and subgroups considered in this work
Equation (7) is applied twice to calculate both pure
compound and infinite-dilution fugaeity coefficients, the
Tableau 1 Liste des groupes principaux et des sous groupesfaisant following relationship can be finally derived for a binary
l'objet de ce rapport
mixture of i infinitely diluted in j:
Main group Subgroup Qk

1: CClaF b CC14 2.910 ln%(j)

(1 ~ ~)7 ' vj/bj-1 _Ai 1+
CF3 1.380 -oj +In - mv/~i 1 ff,.ln 1 ÷bi/v
ibj/vj
CF4 1.840
CC13F 2.644 In %(~j). [ . bj'~
CC1F 2
CC1F 3
1.648
2.100
'
) (13)
CCI2Fz 2.376
which relates the infinite-dilution activity coefficient
2: HCClaF b HCCI3 2.410
HCF3 1.608
at infinite pressure 7~j) to its value 7i(j/at pressure P -~ 0.
HCC1F 2 1.828 Under the same limiting condition, Equation (1) is
quadratic in the volume, so that vi/bi and vj/bj can be
 Prediction of vapour-fiquid equifibria of refrigerant mixtures
Table 2 Results of data reduction for groups in Table 1
Tableau 2 R~sultatsde la compressionde donnOespour les groupes
mentionn~sdans le Tableau 1
Temperature range (K) 172-333
Number of data points
%RMSD
al,2 -330.3
aL1
bL2 103 810
b2,I -9260
obtained by
v 1 -1- 6~+1
Although the experimental value of ~i(j) is available at
P ¢ 0, it can be shown 15 that the influence of pressure on
the calculation of 7i(~) by means of Equation (13) (with
vi/bi obtained from Equation (1)) is negligible for
pressures up to 5 MPa.
Equation (13) is the base equation for the parameter
determination procedure. . The %-~j() values were calcu-
lated by the modified UNIFAC model; note that at
infinite dilution conditions Equation (8) reduces to
ln'y 2) : : uk,,(lnrk,2 - lnr'k, )
k
The values of interaction parameters an,,, and bn,,~ were
adjusted to infinite-dilution activity coefficient data " [ i ( j )
of binary mixtures by means of Equation (13). Unfortu-
nately, only a few data of this kind are available for
mixtures containing only CFCs, HCFCs, HFCs and
FCs 18. Therefore the 7i(j) values were obtained from
reduction of isothermal VLE binary data.
All of the experimental data used, which were selected
from databases 19'2°, underwent a thermodynamic con-
sistency test 21, which is briefly summarized in the
following. Given a binary experimental data point
(P, T, xi, possibly Yi, where i -= 1,2), the corresponding
activity coefficient is given by
yiPcbi
~i- r~vap
AiF i
For the calculation of the activity coefficient "~i a
predictive model is needed. For low to moderate pressure
the correction factor Oi can be estimated through a virial
equation of state, truncated after the second .term, as
suggested by Van Ness and Abbott21:
~i = exp
× I(BVii- v i ) ( p - pvap) + py2(2BVij- B V i i - BVjj)
where BVii and BVij are the pure component and cross
second virial coefficients, which can be expressed as
indicated by Reid et a l .22. With reference to the
553
thermodynamic expression
GE
R T = ~-~xiln'yi (17)
i
61
27.3 activity coefficients calculated by Equation (15) and
substituted into Equation (17) yield values of the excess
82.5 Gibbs free energy G E, which are then fitted to an
appropriate analytical equation giving the composition
dependence of G~. Typically, four- and six-parameter
• 21
Margules equaUons and four- and five-parameter
modified Margules equations z3 were used.
This reduction technique not only was able to perform
a preliminary screening of available experimental data,
checking them out for thermodynamic consistency, but
(14) also allowed a direct evaluation of 'experimental' values
of infinite-dilution activity coefficients, "/i(j)exp, by
applying the pertinent Margules equation in the limiting
condition of x~ --, 0 and x I ~ 1. Thus each data set
provided two values of isothermal infinite-dilution
activity coefficients. The number np of points eventually
selected is reported in Table 2 together with the overall
temperature range considered. Note that only pairs
comprising the following pure components were con-
sidered: R10, R l l , R12, R13, RI4, R20, R22, R23,
Rl14, R124. Owing to thermodynamic inconsistency,
about 15% of the whole data set was eventually
discarded.
The parameter determination was then carried out by
(8')
minimizing the objective function
np )2
1
fob = ~p ~ " ( l n T i ~u)ca
z...~\ . , , - I n ~i~ /)exp (18)
m= l
where 7i(~))exp is the 'experimental' value at infinite
pressure obtained from "Yi(j)exp by Equation (13), and
"Yi~()cal is the value, calculated by the modified UNIFAC
(Equations (8)-(12))•
In Table 2 the values of best-fit parameters an,m and
bn,m of Equation (12) are also reported, with indication of
the per cent root-mean-square deviation (RMSD) on the
experimental infinite-dilution activity coefficients of the
database.
(15) Results
The method currently proposed can be used for the
calculation and prediction of VLE of binary and
multicomponent refrigerant mixtures in the full compo-
sition range.
In the case of a bubble-point problem with nc
components, the system of equations is given by
I yi-Kixi=O
tic
Zyi_l: 0 (19)
i=1
(16) The equilibrium ratios Ki in Equation (19) are evaluated
by
=~ (20)
554 M. Barolo et al.

13 330
12 - ~ .\ . mm
320
J~mu)m
"~.~m • mm •
11 310
~--~ • •

(I)
i
.
300
m..

¢/) ~ 290
9~ E
280
i
8 i 270 •
T~---I
260
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
x,y x,y

Figure 1 Predictions for the system CFCI2-HCFC22 at
T = 303.15K (experimental data from Maczynski and Niedziela 19)
with interaction parameters set to zero
Figure 1 Pr~visions pour le systkme CFC12-HCFC22 it T = 303,15 K
(donn~es expdrimentales de Maczynski et Niedzielal9), les parambtres
d'interaction ~tant fix~s it zdro
Figure 3 Predictions for the system FC116-CFC115 at P = 1.52 MPa
(experimental data from Gmehling et al. z°) with interaction parameters
set to zero
Figure 3 Pr~visions pour le systbme FC116-CFC115 h P = 1,52 MPa
(donn~es exp~rimentales de Gmehling et al.2°), les parambtres d'interac-
tion btant fixOs it z~ro

301 i=..
12

11
um
tm

11)
L.. 15 ~ " "~ =.-- 10 U •

• m

L-. 9 a •

5 ~ 8
r
I I 7 T ~ l , ]

0.0 0.2 0.4
x,y
Figure 2 Predictions for the system HCFC22-HFC23 at
T = 273.15K (experimental data from Maczynski and Niedziela ]9)
with interaction parameters set to zero
Figure 2 Pr~visions pour le systbme HCFC22-HFC23 h T= 273,15 K
(donn~es exp~rimentales de Maczynski et Niedziela19), les parambtres
d'interaction ~tant fix~s gl z~ro
where ~b~ and q~v are expressed by Equation (7), applied
twice, to the liquid and vapour phases respectively, with
7~ given by Equations (8)-(13).
The VLE calculation can be performed following a
standard procedure as indicated for example by Van
Ness and Abbott 2t.
Many simulations of binary refrigerant mixtures have
been performed, and some examples are provided below;
most of them are completely predictive, in the sense that
the binary systems considered were not included in the
database to which the parameters were fitted.
However, a brief discussion is presented first concern-
ing the definition of Table 1. In fact, as the currently
proposed approach relies on a group-contribution scheme,
the definition of groups and subgroups is of paramount
importance. In a recent version of UNIFAC 2, groups
0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
x,y
Figure 4 Predictions for the system CFC12-HCFC22 at
T = 303.15 K (experimental data from Maczynski and Niedziela 19)
Figure 4 Pr~visions pour le systkme CFC12-HCFC22 it T= 303,15 K
(donn~es exp~rimentales de Maczynski et Niedziela I9)
containing both F and C1 atoms are considered:
chlorinated subgroups appear in main groups number
21, 22, 23, 24 (the difference is the number of CI atoms),
while only part of fluorinated ones are included in main
group number 40. We suspect that such division is
questionable when one needs to calculate VLE of binary
mixtures of two chloro-fluorinated refrigerants: unfortu-
nately, no examples of such systems are provided in the
quoted paper. On the other hand, according to the results
presented in a work by Morrison and McLinden 7, which
deals with azeotropy in refrigerant mixtures, it is possible
to argue that, for all azeotropes experimentally detected
so far, the involved components contain subgroups both
of CFC (or FC) and of HCFC (or HFC) types; when only
either CFC (or FC) or HCFC (or HFC) groups are
present in the mixture, a non-azeotropic behaviour is
usually detected. As the recalled division of UNIFAC
includes subgroups both with and without a hydrogen
 Prediction of vapour-fiquid equilibria of refrigerant mixtures 555

Table 3 Predictions for the system HCFC23-CFC13 at T = 199.72K (experimental data from Maczynski and Niedziela16)
Tableau 3 Pr+visions pour le systrme HCF23-CFC13 ~ T = 199,72 K (donnees exprrimentales de Maczynski et Niedziela 16)

Pexp Pcalc
x Yexp Ycalc Ay x 102 (bar) (bar) A p / p x 102
0.0000 0.0000 0.0000 0.00 1.543 1.523 1.30
0.0485 0.1416 0.1606 1.90 1.740 1.747 0.402
0.0868 0.2074 0.2396 3.22 1.839 1.873 1.85
0.1472 0.2909 0.3215 3.06 1.953 2.013 3.07
0.2126 0.3430 0.3789 3.59 2.044 2.108 3.13
0.2507 0.3760 0.4039 2.79 2.081 2.146 3.12
0.2873 0.3960 0.4242 2.82 2.104 2.174 3.33
0.4120 0.4820 0,4778 -0.42 2.144 2.228 3.92
0.5380 0.5350 0,5231 -1.19 2.159 2.239 3.71
0.5650 0.5480 0,5331 1.49 2.158 2.236 3.61
0.6350 0.5800 0.5612 -l.88 2.143 2.222 3.69
0.6570 0.5910 0.5710 -2.00 2.137 2.214 3.60
0.6675 0.5990 0.5759 -2.31 2.130 2.210 3.76
0.7544 0.6460 0.6243 2.17 2.103 2.157 2.57
0.7839 0.6733 0.6452 2.81 2.076 2.130 2.60
0.8148 0.6912 0.6704 -2.08 2.057 2.094 1.80
0.8538 0.7392 0.7090 -3.02 2.002 2.037 1.75
0.9118 0.8121 0.7869 -2.52 1.902 1.919 0.89
0.9747 0.9252 0.9205 -0.47 1.734 1.727 0.40
1.0000 1.0000 1.0000 0.00 1.641 1.625 0.98

40 . . . . . . . . . . i

~' ~ 333.15 K
30 * 313.15 K
t..
¢tl •l ~ / •
c 293.15 K
• 20 • 273.15 K
I!
I,-- 20 253.15 K
z/
¢/3 /
(3,)
I,.. ,,J
10
m
f ,, 15
! e'~ ' ~i~
,,---, ~ #0 ~¢

0.0 0.2 0.4 0.6 0.8 1.0 ::=

¢/}
x,y

Figure 5 Predictions for the system FC14-HFC23 at T = 224.82 K S

(experimental data from Maczynski and Niedziela19)
Figure 5 PrOvisions pour le syst~me FC14-HFC23 h T=224,83K >
(donn~es exp~rimentales de Maczynski et Niedziela 19)

atom in the same main group, almost ideal VLE

behaviours would be calculated for mixtures made up
within that main group: interaction parameters are
indeed zero inside each main group. A similar result
can be obtained with our method, if the group division of 0 I ' I ' I ' [ ' i
UNIFAC 2 is followed: an example is reported in Figure 1
for the system CFC12/HCFC22, where the calculated 0.0 0.2 0.4 0.6 0.8 1.0
(no-interaction) curve shows large deviation from experi-
mental data. x,y
On the other hand, we have observed that HCFC and
HFC subgroups may be collected together in a unique Figure 6 Predictions for the system HCFC22-CFC114 (experimental
main group, and the same is true for CFC and FC data from Kruse et al. 24)
subgroups: see for example Figure 2, system HCFC22/ Figure 6 PrOvisions pour le systbme HCFC22-CFCI14 (donnOes
HFC23 with only HCFC and HFC groups, and expOrimentales de Kruse et al. 24)
Figure 3, system FC116/CFC115 with only CFC and FC
groups, respectively. In both cases, zero interaction values are not compatible with the application of
parameters were used, but the agreement between UNIFAC.
experimental points and curves calculated by our As a conclusion of previously reported results and
method is satisfactory; note also that total pressure more simulations, the division of groups of Table 1 was
556 M. Barolo et al.
devised, and interaction parameter values o f Table 2
were obtained. By using these tables, V L E calculations o f
binary refrigerant systems were performed. F o r example,
Figure 4 refers to the system C F C 1 2 / H C F C 2 2 already
presented in Figure 1: the i m p r o v e m e n t is remarkable.
Table 3 presents the results for the azeotropic system
H F C 2 3 / C F C 1 3 : prediction o f the azeotrope composition
is good, and deviations in the calculation o f boiling
pressures are within an acceptable range. N o t e that
refrigerant H F C 2 3 is not included in the U N I F A C 2
table. The system F C 1 4 / H F C 2 3 is considered in Figure 5,
showing satisfactory behavior up to 3.5 M P a . Finally,
Figure 6 refers to the system H C F C 2 2 / C F C 1 14 over a
wide range o f pressure an temperature.
The relative R M S D in pressure ( R M S D - P ) for the
whole data presented was 3.91 x 10 -2, while the maxi-
m u m relative R M S D - P was 7.98 x 10 -2 (for the system
R 2 2 / R l 1 4 at 253.15K); the R M S D in v a p o u r composi-
tion ( R M S D - y ) for the whole data was 1.48 x 10 -2, while
the m a x i m u m R M S D - y was 2.28 x 10 -2 (for the system
R23/R13). Therefore, in all the cases examined, the
agreement with experimental data is acceptable.
Conclusions
The prediction o f v a p o u r - l i q u i d equilibria o f mixtures o f
refrigerants can be achieved by coupling an equation o f
state model with a g r o u p - c o n t r i b u t i o n approach. In any
case, the g r o u p divisions of the existing U N I F A C
m e t h o d s have to be modified into a f o r m more suitable
for treating refrigerant mixtures.
Based on a cubic R K S EOS and a U N I F A C - t y p e
model for the excess Gibbs free energy at infinite
pressure, a predictive m e t h o d has been developed and
presented for application to mixtures containing C F C ,
H C F C , H F C and F C subgroups with no m o r e than one
h y d r o g e n a t o m Tables o f groups and interaction
parameters have been provided.
Several examples have been reported for binary
systems. The calculated curves reproduce satisfactorily
the experimental behaviour and ensure similar perfor-
mances as equations o f state with classical mixing rules,
but with interaction parameters adjusted on binary data.
A l t h o u g h the m e t h o d needs to be tested for m o r e
systems and extended to different functional groups, it
proved to be an interesting and reliable tool for mixture
screening in refrigeration applications.
Acknowledgement
One o f the authors (M.B.) would like to thank the C N R
- Istituto per la Tecnica del Freddo, P a d o v a - for
financial s u p p o r t
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