ESTIMATION OF PARAMETERS F R THE O NRTL EQUATION F R EXCESS GIBBS ENERGIES OF O STRONGLY NONIDEAL LIQUID MIXTURES

H E N R l R E N O N A N D

J .

M. P R A U S N I T Z

Department of Chemical Engineering, University of California, Berkeley, Calif. 94720

Charts are given for estimating NRTL (nonrandom, two-liquid) parameters from limiting activity coefficient data or from mutual solubilities. Calculated and experimental results are given for binary and ternary systems.

FOR quantitative studies on nonideal properties of liquid

mixtures it is convenient to express these properties with excess functions. For liquid mixtures a t modest pressures remote from critical conditions, the excess functions are insensitive to pressure; a t constant temperature, therefore, the excess functions of such mixtures depend only on liquid composition. The excess Gibbs energy is the excess function of primary interest in chemical engineering and numerous proposals have been made for relating the excess Gibbs energy to liquid composition; the best known, perhaps, are those by Margules and van Laar. A generalization of such proposals was made over 20 years ago by Wohl (1946), but more recently it has been shown that some useful relations for the excess Gibbs energy could not be obtained from Wohls generalization. I n particular, Wilsons local composition concept (1964) resulted in an equation qualitatively different from those proposed earlier. The local composition concept provides a convenient method for introducing nonrandomness into the liquid-mixture model. Wilson (1964) and Orye and Prausnitz (1965) showed that Wilsons equation is in many respects more useful and more directly applicable to strongly nonideal mixtures than any other two-parameter equation, and a particular advantage of Wilsons equation for binary systems follows from its straightforward generalization to multicomponent mixtures without need for ternary (or higher) parameters. However, as pointed out by Wilson (1964) and Orye and Prausnitz (1965), Wilsons equation also contains some undesirable features; especially important is its inapplicability to liquid mixtures with only partial miscibility. I n an effort to overcome this disadvantage while retaining the useful local composition concept, we have developed a new equation for the excess Gibbs energy based on Scotts two-liquid model of mixtures (1956). This new equation, called the N R T L (nonrandom, twoliquid) equation, was described in detail by Renon (1968), who showed that it appears to be applicable to a wide variety of mixtures for calculating vapor-liquid and liquidliquid equilibria. Robert L. Pigford suggested that the practical utility of the N R T L equation could be enhanced if we made available convenient charts for estimating
Present address, Institut Francais du Petrole, Rueil-Malmaison, France.

NRTL parameters from limited experimental data. A number of such charts are presented here.
NRTL Equation

The NRTL equation for the molar excess Gibbs energy of a binary mixture is a function of mole fractions x1 and x 2 :

where

with
g2 1

= gz,

Equation 1 contains two temperature-dependent parameters, (g12 - gZ2)and (921 - gll), in addition to a nonrandomness parameter, a 1 2 ,which, to a good approximation, does not depend on temperature and can often be estimated with sufficient accuracy from the nature of components 1 and 2 (Renon and Prausnitz, 1968). For some systems it appears that (g~, - gll) and ( g 1 2 - g22) are linear functions of temperature. From Equation 1 the activity coefficients, yl and y2, are obtained by differentiation (see Equations 21 and 22 of Renon and Prausnitz, 1968). The N R T L equation is readily generalized to multicomponent mixtures; the result for such mixtures contains only binary parameters. When experimental phase-equilibrium data are available over a range of composition, the optimum parameters (gzl - g11) and (g12 - gZ2)can be determined by a leastsquares fit. [Such a calculation is tedious but can be performed easily with an electronic computer, as shown by Prausnitz et al. (1967).] However, it is also possible to estimate these two parameters from limiting activitycoefficient data, or, for partially miscible systems, from mutual solubilities.
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NRTL Parameters from limiting Activity Coefficients

The limiting activity coefficients are designated by rl" and y Z . I n many cases these can be obtained by a minimum experimental effort, and for a large variety of mixtures they can be estimated from the correlation of Pierotti et al. (1959). At a given temperature T and a fixed a 1 2 , values of yl"(T) and r Z ( T ) uniquely determine values of parameters 712 and 7 2 1 . T o obtain these param; eters from rl" and y, let

and
712

=S -D

(5)

s
and

%(721

712)

(2)

D
I t then follows that

?4(721

- 712)

(3)

I n Figures 1 to 5, for given values of ( ~ 1 2 , we present 7;) the relations between rl", and S and D. To use Figures 1 to 5 we proceed as follows. First, 2 m experimental or estimated values of rl" and y a t the same temperature must be available. Second, depending 1 on the chemical nature of the mixture, a value of a 2 must be chosen; the values recommended by Renon and Prausnitz (1968) provide a convenient guide. Upon calculating loglo (yPy2m) and log,, (yl"/y2m), Figures l to 5 give values of S and D, which, in turn, yield 7z1 and r12as given by Equations 4 and 5. T o illustrate such a calculation, we consider three systems: ethanol-hexane a t 55" C., methyl ethyl ketonehexane a t 60C., and propanol-water a t 60C. For each

Figure 1. Parameters in NRTL equation from activity coefficients a t infinite dilution for a2 = 0.20 1

Figure 2. Parameters in NRTL equation from activity coefficients at infinite dilution for
a12

0.30

414

I & E C PROCESS D E S I G N A N D DEVELOPMENT

Figure 3. Parameters in NRTt equation from activity Coefficients at infinite dilution for
ai2 =

0.40

Figure 4. Parameters in NRTL equation from activity coefficients a t infinite dilution for
a12

0.47

Figure 5. Parameters in NRTL equation from activity coefficients at infinite 1 dilution for a 2 = 0.30
Small or negative deviations from Raoult's law

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415

Table 1. NRTL Parameters from Limiting Activity Coefficients

System Ethanol(l)-n-hexane(Z) Methyl ethyl ketone (1) -n-hexane(2) l-Propanol(l)-water(2)

a

OC.
55 60 60

T.,

loglor;
1.322 0.565 1.147

log10y2"

a2 1

S
1.940 0.669 1.327

D
0.386 0.286 1.300

g2 - g22, 1 Cal./Mok

gzi - gll, Cul./Mole

6P/Pb 6y'
0.8
0.7 1.7

1.013

0.47 0.20 0.30

1010

1515 630 1735

1.2
0.8 2.1

0.507 0.533

253 18

From Pierotti's correlation. * R.m.s. relative deviation in total pressure x 100. e R.m.s. absolute deviation in vapor male fraction x 100.

1.0

- CALCULATED
,
0

I Or
CALCULATED , o EXPERIMENTAL

EXPERIMENTAL

--

075

075

300

I"
E E
K W

8
050
a
%

200

>
W L K
J

2
0 25

too

OY

I
025

I 0 50
X~~~~~~~

I
0.75

I o
10

00

0.2 L 5

0.50 .
X~~~~~~~~

0.75 A

1.0 O

55" c.

Figure 6. Vapor-liquid equilibria for ethanol-n-hexane

at

Figure 8. Vapor-liquid equilibria for 1-propanol-water at 60" C.

I
I."

n ,

< O

,
CALCULATED EXPERIMENTAL

0.75b

/ '

positions and total pressures (Kudryavtseva and Susarev, 1963, Figure 6; Hanson and Van Winkle, 1967, Figure 7; Murti and Van Winkle, 1958, Figure 8). Agreement between calculated and experimental results is good for all three systems; mean deviations between calculated and observed vapor compositions and total pressures are reported in Table I.
NRTL Parameters from Mutual Solubilities

300

0 1 0

I/

I 0.25

I 0.50
X~~~~~~

I 0.75

1.0

I o

Figure 7. Vapor-liquid equilibria for methyl ethyl ketonen-hexane at 60"C.

For binary mixtures with only partial miscibility, it is possible to estimate NRTL parameters from mutual solubilities a t the same temperature. Let x7 be the mole fraction of component 1 in phase a, where i t is smaller, and let x i be the mole fraction of component 2 in phase b, where it is smaller, such that x?/x! 5 1. For a fixed value of aI2 we may obtain S and D from Figure 9, 10, or 11; the NRTL parameters are then found from Equations 4 and 5. Figures 9 to 11 were prepared by solving simultaneously the equilibrium equations
7% = 7:xih

(6)

of these three binary systems we estimate yl" and 7 ; from Pierotti's correlation, with results shown in Table I. Using the recommended values of a I 2 ,we then obtain, for each system, S and D and finally (g12 g2?) and - gil), as shown in Table I. With these estimated NRTL parameters, y-x and P-x diagrams were calculated over the entire composition range (Figures 6, 7, and 8). Also shown, for comparison, are experimental vapor com416

and
72x2 = 72x2
a a

(7)

and the stoichiometric relations x; x; = 1

and

x? + x; = 1

l & E C PROCESS D E S I G N A N D DEVELOPMENT

I5

D N

- I3 --- ;
0
D

'

05

00 6

I O

I5

20

25 - L o * , o l x g x;1

30

IO

I2

Figure

9. Parameters in NRTL equation from mutual solubilities for

a2 1

= 0.2

15

IO
I

-N

-. .
I

0 -

0
rn
i
1

05

06

IO

I5

20

25
-LoPlo(xp

30

IO

I2

x;)

Figure 10. Parameters in NRTL equation from mutual solubilities for

I3

0112

0.3

DN

10

0 \

-9
01

05

00 6

IO

15

20

25

30

10

I2

Figure 11. Parameters in N R T L equation from mutual solubilities for aiz = 0.4

T o illustrate the use of mutual solubility data we consider the system n-hexane-nitroethane. Using mutual solubility data a t 5" and 25C. reported by Hwa, Techo, and Ziegler (1963) we obtain the parameters shown in Table 11. Assuming linear temperature dependence, we obtain a t 45" C.:
(g12

Calculated and experimental vapor-liquid equilibria for this system a t 45OC. are shown in Figure 12. The r.m.s. (absolute) deviation in vapor-phase mole fraction is 0.002 and the r.m.s. (relative) deviation in total pressure is 0.006. Experimental results are taken from Edwards (1962).
Ternary Systems

- gzz)

= 474 cal./mole

and

(gZ1 gll) = 680 cal./mole -

For an additional illustration of Figures 9 t o 11 we consider the ternary system n-octane-isooctaneVOL. 8 N O . 3 JULY 1 9 6 9
417

<-OCTANE

Table II. NRTL Parameters from Mutual Solubilities

g2 1

g1 2

A
- CPLCULPTED
EXPERIMENTPL
WEIGHT F R 4 C T l O N S

Temp., System
O C .

a2 1

Solubilities rl(in 2) rz(in I)

0.100 0.260 0.095

g2 2,

gll,

Cal./ Mole
930 702

Ca1.l Mole
880 780 1124 1115

n-Hexane(1)nitroethane(2) n-Octane(1) nitroethane(2) Isooctane(1) nitroethane(2)

5 25

0.2 0.2

0.275
0.191

25 35

0.2
0.2 0.2

0.120

5 25

0.2

0.187 0.101 0.206

0.297 0.128 0.305

604 478 759 497

980 1026

Figure 13. Liquid-liquid equilibria in system n-octaneisooctane-nitroethane at 25" C.

E i
W

200

Table 111. NRTL Parameters for Three Binary Systems at 7OOC.

0 0 025 0 50
'HEXANE

-I

1 + 4

100

Ethyl acetate Water Ethanol

Water Ethanol Ethyl acetate

0.4 0.3 0.3

1335 976
301

2510 88
322

0 75

IO
ETMANOL

Figure 12. Vapor-liquid equilibria for n-hexanenitroethane at 45" C.

i /E T H Y L ACETATE

ClLCULATED EXPERIMENTAL

M O L E FR4CT10NS

nitroethane. Mutual solubility data for each binary octane-nitroethane system are given in Table I1 a t two temperatures. From these (using a l p = 0.2) we obtain the NRTL parameters shown. We then proceed to calculate the ternary liquid-liquid equilibria a t 25" C. using the multicomponent form of the N R T L equation (Renon and Prausnitz, 1968) and the assumption that isooctane and n-octane form an ideal mixture. The results of this calculation are shown in Figure 13,along with experimental data of Techo (1962).Further, assuming a linear relation between (9, - gJ and temperature for the system isooctane-nitroethane, we calculated vapor-liquid equilibria for the ternary system a t 35C. When the calculated vapor compositions are compared with experimental values, the r.m.s. absolute deviation is 0.019 mole fraction and the r.m.s. relative deviation in total pressure is 0.033. For a final example, we consider the ternary system ethyl acetate(l)-ethanol(2)-water(3) a t 70" C. The binary parameters used in our calculations are given in Table 111; they were obtained as follows: Mutual solubility data a t 70C. for ethyl acetate-water are given by Griswold et al. (1949);activity coefficients a t infinite dilution for water-ethanol were estimated using Pierotti's correlation (1959); parameters for ethanol-ethyl acetate a t 70" C. and were estimated from limiting activity coefficient data of Murti and Van Winkle (1958) a t 40" to 60C. Figure 14 compares calculated results with the ternary measure418

WATER

Figure 14. Liquid-liquid equilibria in system ethyl acetateethanol-water at 70"C.

ments of Griswold et al. (1949).Predicted ternary properties are in satisfactory agreement with experimental results.
Conclusions

The NRTL equation provides a useful description of the excess Gibbs energies of strongly nonideal mixtures that may or may not be completely miscible. Parameters in the equation may be estimated from limiting activity coefficients or from mutual solubilities; charts to facilitate such estimates are presented. While best results are cal-

I & E C PROCESS D E S I G N A N D D E V E L O P M E N T

culated when the nonrandomness parameter, a12,is determined from experimental data, good results may often be obtained by setting C Y ~ Z equal to a fixed value suggested by the molecular nature of the components.
Acknowledgment

The authors are grateful to the Computer Center, University of California, Berkeley, for the use of its facilities.
literature Cited

Edwards, J. B., dissertation, Georgia Institute of Technology, 1962. Griswold, J., Chu, P. L., Winsauer, W. O., Ind. Erg. Chem. 41, 2352 (1949). Hanson, D. O., Van Winkle, M., J . Chem. Eng. Data 12, 319 (1967). Hwa, S. C. P., Techo, R., Ziegler, W. T., J . Chem. Eng. Data 8,409 (1963). Kudryavtseva, L. S., Susarev, M. P., Zh. Prikl. Khim. 36, 1471 (1963).

Murti, P. S., Van Winkle, M., Ind. Eng. Chem., Chem. Eng. Data Ser. 3, 72 (1958). Orye, R. V., Prausnitz, J. M., Ind. Eng. Chem. 57, No. 5, 18 (1965). Pierotti, G. J., Deal, C. A., Derr, E. L., Ind. Eng. Chem. 51, No. 1, 95 (1959). Prausnitz, J. M., Eckert, C. A., Orye, R. V., OConnell, J. P., Computer Calculations for Multicomponent Vapor-Liquid Equilibria, Prentice-Hall, Englewood Cliffs, N. J., 1967. Renon, H., Prausnitz, J. M., A.I.Ch.E. J . 14, 135 (1968). Scott, R . L., J . Chem. Phys. 25, 193 (1956). Techo, R., dissertation, Georgia Institute of Technology, 1962. Wilson, G. M., J . A m . Chem. SOC. 127 (1964). 86, Wohl, K., Trans A.1.Ch.E. 42, 215 (1946). RECEIVED review November 11, 1968 for ACCEPTED March 21, 1969 Work supported by the National Science Foundation.

HIGH TEMPERATURE PYROLYSIS OF ISOBUTENE

K A R L S C H U G E R L A N D
JOHN H A P P E L

Chemical Engineering Department, New York University, Bronx, N . Y .

The product distribution of the high temperature pyrolysis of isobutene was experimentally determined. The decomposition can be represented as a system of simultaneous and/or consecutive reactions.

METHYLACETYLENE and/or allene can

be obtained by pyrolysis of isobutene (2-methylpropene) or propene. Rice et a / . (Rice, 1948; Rice and Wall, 1950; Rice et al., 1948) and Szwarc (1949) were among the first to report the synthesis of methylacetylene and/or allene by the pyrolysis of isobutene. Szwarc (1949) and later Sakakibara et al. (Kunichika et al., 1965; Sakakibara, 1964) and Amano and Masao (1964) investigated the pyrolysis of propene. A number of patents (Happel and Marsel, 1956, 1962; Hogsed, 1959, 1960; Keith et al., 1961; Rice, 1948) deal with the industrial application of these reactions. Radical sources can be used to increase the yield of methylacetylene and/or allene (Happel and Marsel, 1965; Peer and von Lohiuzen, 1958). The pyrolysis of isobutene has not been reported a t temperatures above 1000C. and very short reaction times. I n this study, isobutene, as well as allene, methylacetylene, and propene, which are intermediate decomposition products of isobutene, were pyrolyzed by admixture with hi,gh temperature steam.
Experimental

High temperature steam was generated by means of a hydrogen-oxygen torch and diluted with low pressure secondary steam. The olefin to be cracked was introduced
I Present address, Institut fur Chemische Technologie, T.U., 33 Braunschweig, Hans-Sommer-Str. 10, Germany.

from above the reaction section. The reaction mixture was quenched rapidly by means of water sprays a t the bottom of the reactor. The pyrolysis equipment (Figure 1) consisted of a hydrogen-oxygen torch, a, a water-cooled zirconia-lined high temperature steam generator, b, a 5-p.s.i.g. steam inlet section, c , an olefin inlet section, d , a reactor, e, with the quenching section, f , a knockout tank, g , packed with steel wool, liquid gas separators, h, a gas meter, i, and a sampling device, j . The steam superheater, k , olefin preheater, 1, and steam line trace were warmed prior to use. The reactor was flushed with nitrogen, and the spark plug igniter, m , dried. Water to the quenching sprays, cooling jackets, and water seals was turned on. The igniter was started and first the oxygen and then the hydrogen check valves were opened. When the flame was stabilized, the secondary steam was turned on and the amount of hydrogen-oxygen mixture as well as the ratio of hydrogen to oxygen was gradually increased. A slight excess of hydrogen was used to avoid burning the olefin. The desired temperature was maintained by a proper ratio of primary and secondary steam. When the olefin flow rate was established for the run, the nitrogen flow was stopped. The temperature i~ the reactor was measured a t three positions by P t - P t / I r thermocouples, p . Flow rates were determined by rotameters, q. Volume of effluent gas was measured by a gasmeter, i. A bypass protected meter i during starts
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