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February 1948

y,, 7 2 = activity coefficients

I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
(3) Benedict,
Trans. Am. Inst. Chem. Engrs., 41,371 (1945).

345

M., Johnson, C. A,, Solomon, E., and Rubin, C. C.,

Vl, Vz = molal volumes of the liquid components V , = molal volume in the gaseous state B = second virial coefficient Po, To = critical pressure and temperature

= an arbitrarily fixed temperature s = slope factor, Equations 11 and 12 (Y = relative volatility


LITERATURE CITED

(1) American Petroleum Institute Research Project 44, National Bureau of Standards, Selected Values o f Properties of Hydrocarbons, Tables 2k (March 31,1944) and 5k (June 30, 1944). (2) Beatty, H.A,, and Calingaert, G., IND. ENG. CHEH.,26,504,904 (1934).

(4) Brunjes, A. S.,and Bogart, M. J. P., IND. ENG.CHEM., 35,255 (1943). (5) Lewis, G.N., and Randall, M., Thermodynamics, New York, McGraw-Hill Book Co., 1923. (6) Othmer, D. F., and Benenati, R. F., IND. ENQ.CHEM., 37, 299 (1945). and Raymond, C. L., J . Am. Chem. SOC., 60,1278. (7) Scatchard, G., (1938). (8) Tongberg, C. O., and Johnson, F., IND. ENG.CHEM.,25, 733 (1933). (9) York, R., and Holmes, R. C., Ibid., 34,345 (1942).
RECEJVED November 26,1946.

(Thermodynamics of Nonelectrolyte Solutions)

ALGEBRAIC REPRESENTATION OF THERMODYNAMIC PROPERTIES AND THE CLASSIFICATION OF SOLUTIONS


OTTO REDLICH
AND

A. T. KISTER

Shell Development Company, Emeryville, Calif. T h e utilization of laboratory data for the design of distillation columns and other separation equipment requires the efficient representation of extensive experimental data. A flexible, nonarbitrary, and convenient method is developedfor systems of two or more components. This method furnishes an immediate distinction between various types of solutions.

XPERIMENTAL results can be improved or damaged on their way from the laboratory to the practical application. in plant design and operation. The treatment of experimental data should eliminate inconsistencies without distorting the results by imposing arbitrary conditions, it should be flexible enough to cover all important cases, and it should be pimple in operation, From this viewpoint the following method was developed for the representation of thermodynamic properties o f nonelectrolyte solutions. The present discussion starts from binary solutions and is later extended to systems of more components.
SELECTION OF A USEFUL FUNCTION

a = y(1

- z ) / x ( l - y)

(4) (5)

for log a = log ( Y l l r n ) -I- log (PYP,) where g is the mole fraction in the vapor and p i and p i are the vapor pressures of the pure components, the vapor being 118sumed to be perfect. Furthermore, the function log (-y~/r~) provides an efficient tool for eliminating inconsistencies in the experimental data. Since &, according to Equation 1, assumes the value zero for x = 0 and x = 1, we derive from Equation 2

The use of the activity coefficients y1 and y 2 is not advisable since they are redundant. The use of two functions necessitates the imposition of a condition-namely, Duhems equation. This complicates any correct smoothing procedure. For this reaeon Scatchards excess free energy is preferable. Dividing this function by 2.303RT, one obtains

= x log YI

+ (1 -

Z) log

-i2

(1)

(z mole fraction of the first component) , which y a y be considered a little more convenient in some numerical calculations. * For various reasons still more suitable is the function dQ/dx = log
( Y I ~ Y ~

Figure 1 shows a simple example for the application of this condition. The only curve for log (rl/r3which represents the data in accordance with Equation 6 is the iero line-that is, the system is perfect within the limits of experimental error. The deviations for low concentrations of either component are safely recognized t o be due to experimental errors. One could hardly arrive so quickly and cogently at the same result by another method. The relation

(2)

(7)
following from Equations 5 and 6 is sometimes useful. If the values of .(Y r:fer to a constant temperature, the integral is equal to log ( p l / p z ) . If (Y is derived from equilibrium measurements over a moderate temperature interval, the integral can be easily estimated since usually varies only little with the temperature. Equation 7 is based only on the assumptions that the vapor is perfect and that the dependence of the activity coefficients on the temperature may be neglected.

The degree of this function is one unit lower than Q as well as the functions log 71 = Q

+ (1 - s)dQ/dx

and log y~ = Q

- xdQ/dx

(3)

This is a considerable advantage in practical calculations, realized in a special case already by Benedict et al. (1). Another advantage of the function log (y1/y2) is its simple relation to the experimental data and to the technically important relative volatility :

INDUSTRIAL AND ENGINEERING CHEMISTRY

voi. 40, No. 2

Figure 1. 2,2,4-Trimethylpentan~Methylcyclohexane at 741 Mm.


Measurements of Harrison and Berg (3). Zero line represent. perfect solution.

SERIES DEVELOPMENT

of functions like Q, log y, etc., into power aeries with respect to x has been suggested already by hlargules. Por nonelectrolytes it is always permissible and at least in numerous cases useful. The usefulness, however, depends greatly on the form of the series. Kohl ( 7 ) , in reviewing the various methods of representing activity coefficients, pointed out that the series should be developed in such a way that the higher. terms are oorrections of the terms of lower order. In this way he avoids the inconvenience of having the result appear as a small difference of large terms. Also important is the fact that the coefficients of a properly chosen series furnish a natural classification of various systems, as will be s h o m later. Since Q = 0 for x = 0 and x = 1, each term must contain the factor x(1 - 2). It is desirable to develop the series with respect to a variable which is somehow symmetric with respect to the two components. The simplest variable of this kind is 22 - 1, which merely changes its sign on exchange of the components. Thus the most useful development appears to be

The development

= ~ ( ls ) [ B

+ C(22 - 1) + D ( 2 2 - 1)' +

(8)

The coefficients are determined either by plotting

= 0, is represented by a straight line in a diagram of log(yl/r2) against x. This straight line must, according to Equat,ions 6 or 10, pass through zero at x = 0.5. TYPE3. The type B # 0; C # 0 ; D = . . . = 0 corresponds to what is frequently called t'he equation of ?vlargules. If a large number of experimental points of extremely high accuracy is to be represented, the method of least squares with properly chosen weights will be adopted for the determination of the constants B and C. In general, however, the following method furnishes in a few minutes the best results. The method consists of plotting the experimental data for log(yl/yz) against 2 , drawing a preliminary curve, and reading the values of log(yl/yz) for a number of characteristic points listed in TableI. For type 3-that is, D = &only points 1, 3, 5, 7, and 9 need be considered. In points 3 and 7 the value of log(yl/yJ is independent of C. In addition, the values of the function in these two point,s are equal if three terms are sufficient in Equation 10. This condition may be assumed to be satisfied in all cases except for extreme deviations from the perfect solution-that is, especially for incompletely miscible systems. The equality of the values of log(yl/rt) for p0int.s 3 and 7 constitutes, therefore, in many cases, a check of the experimental data. The value of B - D / 3 , or, if D = 0, of B, is calculated from the best value of log(yl/y2) for point,s 3 and 7. The value of C is derived from point 5 . If D = 0, the quitntities ( B C) and ( - B C) must represent reasonable values for points 1 and 9. 9new curve is drawn through the points 1, 3, 5, 7, and 9 calculated according to Table I with the assumed values of B and C. The deviations of the experimental points from this curve are to be judged with regard to Equation 6-that is, only such variations of the representative curve are permissible which do not change the total area under the curve. With a little practico one sees immediately whether a slight adjustment of B and C will improve the agreement. TYPE 4. The type B # 0, D # 0, and c = 0 actual1,y exists. Several systems of methanol and hydrocarbons can bo approximately represented by a corresponding function. The diagram of 1og(y1/y2) indicates this type immediately by the S-shape of the representative curve. The absolute values of the function at, z = 0 and x = 1, are equal, and the curve passes through zero a,f,x = 0.5. The values of B and D are easily derived from points 2, 4,6, and 8 (Table I). TYPE 5 , If none of the constants B, C, and D equals zero, C is calculated from point 5 (Table I), B from points 2 and 8, and D from point,s 4 and 6 in which the value of t'he 11 term reaches a maximum.

or, preferably, from a diagram of

DISCUSSION O F TYPES

+ D ( l - 2.r)ll - 8 r ( l - z)] +
TYPES OF SOLUTIONS

(10)

TYPE1. The simplest case is the perfect solution for which log(r,/rz) = 0. TYPE 2. The next type, characterized by B # 0; C = D = . . ,

A principal advantage of a classification like that discussed in the preceding section lies in its close connection with the nature of the solutions and of the components. It is well known from the work of Hildebrand, Scatchard, Guggenheim, and others that type 2 very well approximates systems the components of which are not associated, interact only moderately, and have approximately equal molal volumes. For systems which do not satisfy the last condition, Scatchard ( 5 ) suggested the relation (Equation 11).

TABLE I. CHARACTERISTIC POINTS


h-0.
1
B
0 -; +D

2
0.7071B 8 -0.7071B
0.1464

f ,
NO.

- C/4

fog ( y I / y I )

- B -1C - D

0.8536

- C/4

7 0.7887 -0.5773 (B- D / a )

3 0.2113 0,5773 ( B D/3)

0,2969 0.4082 ( B 21)/3) 6 0.7041 -0.4082 ( B 2 0 / 3 )

+ C/4
+ C/4

5 0.5

c/2

../ ... ...

February 1948 2.303RTQ = AViVzX(1

I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY

341

- z)/[xVI

+ (1 - x)VZ]

(11)

where Vi and V2 are the molal volumes of the components. If this equation is developed into a series similar to Equation 10, the comparison of the coefficients furnishes

The development of Q into a power series can be appropriateIy generalized without difficulty. It is useful to rewrite Equation 8 in the more symmetric form
Qlz

ZIXZ[BIZ Clz(~1

- 2,) + DIZ(ZI- X Z ) ~+ . . .I
Q3i Qiz

(17)

B = 2AViV2/2.303RT(Vl f V z ) C - B(Vi - Vz)/(Vi Vz) D = B(Vi - VdZ/(V1 Vz)'

+ +

The series for a ternary system is then conveniently represented by (12)

212223

[C

Q + + + D i ( ~ z- + D2(23 - + . . . I
Q23 ~ 3 )

21)

(181

The D term contributes less than 0.011B to log(yl/yz) if the larger molal volume exceeds the smaller by less than 50%. Scatchard's equation therefore can be replaced in this case for data of moderate accuracy by a formula of type 3 with the value of C given in Equation 12, This formula is usually more convenient than the original equation. Figure 2 illustrates ?n application of this formula. Scatchard's equation has been found to approximate well all hydrocarbon eystems except those containing benzene. It will be shown in another paper of this series that association of one of the components produces a contribution to log(-yi/rz) which has approximately the character of the ll term in Equation 10. Types 4 and 5 therefore will be discussed in connection with association. A few results, however, should be anticipated here. Interassociation between the two components tends to diminish the influence of the term characteristic of association. This explains why systems of highly associating substances often belong to type 3. The association term is maintained if both components associate but not with each other, Apparently the system benaenecyclohexane belongs to this type. According to Hildebrand (4) both substances are slightly associated. The measurements of Scatchard, Wood, and Mochel(6) can be represented by Equation 10 with a finite value of D. It should be pointed out, however, thab the existqnce of this small D term could be ascertained only by measurements of high accuracy. Within the limits of error of the usual technique the system would belong to type 3 rather than type 5. Thus the classification presented here furnishes approximations of various degrees. This flexibility may be considered to be an advantage of a power series.
MULTICOMPONENT SYSTEMS

The number of coefficients required for a series running to a certain degree has been discussed by Benedict et al. ( I ) . The present representation offers again the advantage of a natural classification by means of terms of decreasing importance. Equations 16, 17,and 18 furnish for a ternary system log
(7z/7i) =

+ DlZ(Z1 - XZ)[(Xl - - 4x12221 + . . . + - B81 f Cz3(222 - + c31(221 + Dz8(32s2 - 4x228 + - D31(32l2 - 42123 + + - + D1(-2321 f 2x122 + - zZZ) + +23zl + 22122 - - f . . I
22)2

Blz(21 -

22)

+ Cm[3(21 23)

2z)*

11/2

23[B23

23)

23')

23')

c(Zl

22)

22x3
s

02(

22x3

Xiz)

(19)

The actual calculation is simple, since the higher terms are always small and often negligible. Cyclic permutation of the subscripts furnishes log(7 3 / 7 2 ) and log(y~/y,~). For a system of four components Q is represented by the sum of the six binary functions of Equation 17, the four terms containing 21x223, etc., and a term containing X I X Z X ~ X P . The further generalization is obvious. EXAMPLE: ~HEPTANE-METHANOL-TOLUENE. The measurements of Benedict et al. ( I ) of vapor-liquid equilibria in the system n-heptane-methanol-toluene furnish an opportunity to show that even accurate measurements in a ternary system can be sufficiently well represented by the functions Q for the binary systems alone, provided that adequate expressions for these systems have been found. Systems with an associating component like methanol are properly represented by means of the association function

A ( K , x ) = 22 log (1 210g (1 22

+ 11 + 4 K ~ ( l- ~)]')2)/'2(1-

+ K) -

2)

(20)

The series used for binary systems can be extended without difficulty to multicomponent systems. The definition of the function Q by Equation 1is now replaced by

0 . 1 00

= X Z log ~ ~k

t
0.05

(13)

The relation of this function with the free energy furnishes for the activity coefficient
I

The differentiation is to be performed at constant pressure and temperature. Also, all mole fractions are to be kept constant except the one indicated in the differential quotient. It is convenient for some calculations to represent Q as a sum of terms Q h which are homogeneous of the degree h in the mole fractions xk. Equation 14 can then be written as log The functions log (rr/y*) = a Q / a ~ r- aQ/axa (16) offer the same advantages as the function defined in Equation 2. Their degree is one unit lower than that of 6 ? or logy?,and they are closely connected with the relative volatility.
y r = ZBQh/aXr

t 2
h

- 0.05
-0.1

- f(h - 1)Qh

'

(15)

1
0

0.5

Figure 2.

Toluene-2,2,4-Trimethylpentane at 760 Mm.


Curve

Menmaremento of Driakamar, Brown, and White ( 3 ) . repremntm Santahard'a equation.

348

INDUSTRIAL A N D ENGINEERING CHEMISTRY


coefficients-namely,

Vol. 40, No. 2

TABLE 11. RELATIVE VOLATILITY OF ~-HEPTANE-~~ETHAN derived O L from the ternary system. The practical importance of A T 760 AIM. the restriction of the number of empirical coefficients need not be
1,

eight from the binary jystems and three

oc.

x2

Obsvd.

60.60 59.47 58.93 58.82 58.81 59.01 59.90

0.138 0.178 0,390 0.668 0.810 0,885 0.946

RIethanol/Heptane Benediet This paper 16.1 16.45 16.5 12.6 12.65 12.55 4.43 4.45 4.36 1.46 1.49 1.47 0.696 0.691 0.702 0,423 0,407 0.419 0,242 0,243 0.246

strrssed
CONCLUSIBSS

TABLE 1 1 1 . RELATIVE VOLATILITY OF


AT
t,

>\IETHBSOL-TOLCENF:

760 MM.
Obsvd.

oc.

22

RIethanol/Toluene Benedict This paper 15.07 9.75 5.72 3 07 2.17 1.65 1.19 0.99 0.80 0.62
.

70.25 66.44 65.58 64.47 64.10 63.79 63.67 63.58 63.62 63.94

0.130 0.266 0,407 0.593 0.692 0.779 0,843 0,852 0.927 0,969
~

19.0 9.90 5,94 3.10 2.16 1.54 1.23 1.01 0.81 0.61
~

17,s 9.83 5.93 3.13 2.20 1.58 1.21 1.01 0.80 0.81

The use of the funct'ion log(rl/rz) for the representation of free energy data of binary solutions is advisable. A suitably chosen power series represents this function in a flexible and unbiased ~ i a y . The coefficients can be derived quickly from rxperimental data. The nature of various classes of solutions is expressed in the magnitude of these coefficients. The behavior of log(y , / y 2 ) therefore can be predicted to a certain degree. Scatchard's cquation furnishes a good approximation for systems of hydrocarbons except those containing benzene. The series used for the free energy can be advantageously used also for other propertie., such as heat content and entropy.
ACKNOWLCDGIIENT

--

TABLE 1 1 ' .
t, ae.
90.77 69.96 61.59 59.97 m61.35 82.01 64.34 62.96

RELATIVE \70L.ITILITICY
El
I 2

OF n - I l c P . r . ~ ~ ~ - - 1 ~ ~ T H , 4 ~ O L - - T n L .4T U~ 760 SE

lIA>I,

0.0684 o.1.51.0 0.0787 0.3412 0.1717 0.0911 0.0962 0.2533

0,8486 0.7733 0,7494 0.5409 0.6038 0,6114 0,3711 0,3172

Heptanc/Toluene Ohsvd. Bencdict This paper 2.75 2.78 2.72 2.11 2.26 2.32 2.58 2.63 2.48 1.65 1.8 1.83 2.07 2.17 2.08 2.43 2.42 2.25 2.24 2.13 2.04 1,85 1.92 1.82

I n tkis equation the mole fract,ion z refers t o the associating characteristic Of this component' component, and is a 'Onstant The three binary systems have been found to be represented bv means of the coefficients (1 = heptane, . 2 = methanol, 3 = toluene)
B 2 3

A., Solomon, E., a n d Rubin, L. C., Trans. Am. Inst. Chem. Engrs., 4 1 , 371 (1945). ( 2 ) Drickarner, H. G., Brown, G. G., and IVhite, R. R., Ibid.,

IIcthanol/Toluene Obsvd. Benedict Thiq paper 1.15 1.19 1.24 1.58 1.64 1.80 1.91 1.77 1.88 3.8 3.9 4.20 3.22 3.25 3.26 3.13 3.06 3.08 7.14 6.8 6.92 8.3 8.5 8.6

The authors cxpress their gratitude to It. W. Millar and G. Muller for helpful discussions on t,he subject of this and the preceding paper. L. Korba assisted the authors in the calculations.
LITERATURE CITED

(1) Benedict, M., Johnson, C.

0.95;

Bai

0.117; 0.018;

Biz = 1.178
D 1 2 =

41, 555 (1945). Est, CHEM., 38, 117 (1946). (3) Rarrison, J. M , , andBerg, L,, IND, (4) Hildehraild, J. H., J . them. phys., 7, 234 (1939). (5) S c a t c h a r d , G., Chem. Revs., 8, 321 (1931). (6) S c a t c h a r d , G . , JVood. S. E., and Moohel, J. M., J . P h ~ s Chem., . 43, 119 (1930). ( 7 ) Wohl, K., T,.ans. Am,. h t . C'hem. Eiigis., 42, 215 (1946).
RECEIVED

Kz = 3.8;

c 3 1 =

0.155

(21)

November 2 5 , 1946

ail other coefficients being zero. Accordingly, the followingequations were used for the ternary system:

log

(?1/?'3) = 02 2 8 ~ ~ O.117(x3 - xi)

-k Z a ( Z 8 -

2Z1)]

+0 Ol8[z,(~ -~ 2s3) + 0.155~2(3~: +


4ZlXz

2:)

(23)

The corrections for the imperfection of the vapor calculated by Benedlct et at. ueie used. The results are compared n ith the experinlental and calculated values of BenediLt el al in Tables 11, 111, and IV. These tables contain the temperature, the mole fractions in the Irqurd, and the relative volatilities observed and calculated by Bcnerhct et al. and by means of Equations 22 and 23. The volatilities calculated by mean3 01 these equations agree with the observed values approximately a5 well as the values calculated by Benedict et al.; but Equations 22 and 23 contain only six coefficients, all derived from the binary systems. Bonedict et d. introduced eleven

Furfural Solvent Extraction Unit for Lube Oil

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