Ind. Eng. Chem. Process Des. Dev., Vol. 17, No.

3, 1978 371

k e = effective thermal conductivity of catalyst particle,

cal/(cm)(s)("C) m = generalized Thiele-type modulus, defined by eq 18 R = rate of disappearance of reactant, mol/(s)(g of cat.) R, = gasconstant r = radial coordinate in catalyst particle, cm r' = dimensionless radial coordinate, r/ro ro = radius of catalyst particle, cm S = outer surface area of catalyst particle, cm2 T = temperature, K U = function of a , 6 , and y, defined by eq 20 V = volume of catalyst particle, cm
Greek Letters = dimensionless parameter, k z / C ~ , , /3 = dimensionless parameter, (De)B/b(De)A y = dimensionless parameter, C A , ~ / C B , ~ 7 = effectiveness factor $ = Arrhenius number, EIR, T, t = dimensionless parameter (-AH)(De)BCB,s/ke T s p = apparent density of catalyst particle, g/cm3 4 = Thiele modulus for intrinsic kinetics of eq 1,oxidation kinetics, defined by eq 12 4 h = Thiele modulus for half-order kinetics, defined by eq 16 4~~ = 4 with k l evaluated a t T,; i.e., eq 26
LY

B = reactant B (oxygen) s = outer surface of catalyst particle

11, 351 (1965). Carrahan, B., Luther, H. A,, Wilkes, J. O., "Applied Numerical Methods," Wiley, New York, N.Y., 1969. Chu, C., Hougen, 0. A,, Chem. Eng. Sci., 17, 167 (1962). Goto, S., Levec, J., Smith, J. M., Catal. Rev. Sci. Eng., 15 (2), 187 (1977). Levec, J., Smith, J. M., AlChEJ.. 22, 159 (1976). Levec, J.. Herskowitz, M., Smith, J. M., AIChEJ., 22, 919 (1976). Look, K., M.S. Thesis, University of California, 1977. Paterson, W. R.. Cresswell. D. L., Chem. Eng. Sci.. 26, 605 (1971). Roberts, G. W., Satterfield, C. N., lnd. Eng. Chem. Fundam., 4, 288 (1965). Roberts, G. W., Satterfield, C. N., Ind. Eng. Chem. Fundarn., 5 , 317 (1966). Schneider, P., Mitschka, R. A., Collect. Czech. Chem. Commun., 30, 146 (1965a). Schneider, P., Mitschka, R. A.. Chem. Eng. Sci., 21, 455 (1965b). Schneider, P., Mitschka, R. A., Collect. Czech. Chem. Commun., 31, 1205, 3677 (1966). Voikman, Y. M., MSc. Thesis, Israel Institute of Technology (Technion), 1967. Villadsen, J. V., Stewart, W. E., Chem. Eng. Sci., 22, 1483 (1967). Weisz, P. B., Hicks, J. S., Chem. Eng. Sci., 17, 265 (1962).

L i t e r a t u r e Cited Bischoff, K. B.. AlChEJ.,

Department of Chemical Engineering University of California Davis, California 95616

Kevin Look J. M. Smith*

Received for review February 2,1977 Accepted January 9,1978

Subscripts A = reactant A (oxidizable substance)

Supplementary Material Available: Additional numerical solution (including two graphs) of effectiveness factors (8 pages). Ordering information is given on any current masthead page.

Correlation of Wilson Parameters with Number of Carbon Atoms for Primary Alcohol-Aromatic Systems

Wilson parameters for binary systems containing primary alcohols and benzene or toluene have been determined. The temperature dependence of each parameter was expressed in a quadratic expression involving the coefficients and the temperature. Further, these coefficients were related to the number of carbon atoms in the alcohol, indicating the feasibility of eventual extrapolation of the data by group contribution or other methods. In the development of the values of the parameters isothermal and isobaric VLE and heat of mixing data were used. The Powell optimization algorithm and the objective function of Nagata and Yamada, involving both excess free energy and excess enthalpy, were employed.

xi + A 1 2 ~ 2

where A'ij = dAij/d(l/T). Values of the activity coefficients were calculated from P-T-n-y data as

gEIRT =

-[XI

In

(XI

+ x2A12) + x 2 In (x2 + xlhzl)]

(1)

0019-7882/78/1117-0371$01.00/0 0 1978 American Chemical Society

21fi12x

At the present, the Wilson equation (1964) is perhaps the most widely used expression for the prediction and correlation of vapor-liquid equilibrium (VLE) data. In addition, several investigators (Asselineau and Renon, 1970; Duran and Kaliaguine, 1971; Nagata and Yamada, 1973) have also extended the Wilson equation to correlate heat of mixing data. The purpose of this work is to calculate the Wilson parameters of binaries containing homologues of primary alcohols and benzene or toluene and to study the relationship of these parameters to the number of carbon atoms of the alcohol. Both VLE and heat of mixing data were used to calculate these Wilson parameters. The temperature range of the data studied extended from 25 "C to the normal boiling of the less volatile component present. The Wilson equation as modified by Orye and Prausnitz (1965) for a binary mixture is

where

From eq 1,the activity coefficient and heat of mixing are shown as eq 3 and 4

hE =

)- (
x2 x2

'lAfZ1

+ Azlxl

(4)

372

Ind. Eng. Chem. Process Des. Dev., Vol. 17, No. 3, 1978

Table I. Data References Alcohol Methanol Ethanol Propanol Butanol Pentanol Methanol Ethanol Propanol Butanol Pentanol Data references (A) Alcohol(l)-Benzene(2) Systems Scatchard et al. (1946), Strubl et al. (1972), Shirai et al. (1965), Nagata (1969) Smith and Robinson (1970), Brown and Smith (1954), Udovenko and Fatkulina (1952), Nielsen and Weber (1959),Maripuri and Ratcliff (1972) Brown and Smith (19591, Fu and Lu (1966),Wehe and Coates (1955) Brown and Smith (1954), Vijayaraghavan e t al. (1965), Mann et al. (1963) Wehe and Coates (1955) (B) Alcohol(l)-Toluene(2) Systems Lu (1957) Van Ness e t al. (1967), Landwehr et al. (1967) Lu (1957) Seetharamaswamy et al. (1969), Sadler et al. (1971) Sadler et al. (1971)

The values of six X ' s were determined by minimizing the following objective function by using the Powell (1964) optimization algorithm (Brinkman et al., 1974).

Data Sources
The pure component properties, vapor pressure-temperature relationship, volume-temperature data, and critical temperature and pressure were obtained from Kemme and Kreps (1969), Perry (1963), Rossini (1953), Timmermans (1950, 1965), and Weissberger et al. (1955). Heats of mixing for alcohol-aromatic systems are reported by Mrazek and Van Ness (1961) and Van Ness et al. (1967). The sources of the binaries data are reported in Table I. The data for the pentanol-benzene system were found to be inconsistent through testing with the Gibbs-Duhem equation. Carbon Number Correlation Systematic variation of calculated X's with accession of carbon number in alcohol homologue led to the use of X as a quadratic function of carbon number C X ( n ) = AnO

Table 11. Carbon Number Coefficients for Temperature Coefficients

Ai0 A20 A30

= 2370.94500 = -2.68710

A40 A50 A60

= =
= =

(A) Alcohol-Benzene Systems A12 = 60.89859 A11 = -481.17360 A21 = -0.17716 A22 = -0.15280 A32 = -0.00592 0.01226 A31 = -0.02963 A41 = 34.11961 A42 = -3.51465 145.19380 A52 = 0.01326 0.54493 A51 = -0.38084 -0.01235 A61 = 0.01085 A62 = -0.00191 (Bj Alcohol-Toluene Systems A11 = -403.90920 A12 = 29.92752 A 2 2 = 0.21102 A20 = -1.47406 A31 = 0.00414 A 3 2 = 0.00050 A41 = 25.34299 A42 = -1.68501 A51 = -0.13060 A52 = 0.01088 A61 = 0.00388 A62 = -0.00043

Aio A20 A30 A40 A50 A60

= 2563.46600 = -2.91714 = -0.00096 = 138.13820 = 0.58236 = -0.01349

+ AnlC + An2C2

(10)

These coefficients A's for alcohol-benzene and alcohol-toluene binaries are summarized in Table 11. By using T - 273.15 = 25 "C in eq 7 and 8, values of energy parameters are shown in Table 111. Mean deviation of heats of mixing and compositions are also listed. Systematic variation with molecular size of alcohol is indicated. Acknowledgment The authors wish to acknowledge financial assistance from the Engineering Research Center of the University of Nebraska. Nomenclature A = coefficients in eq 10 C = carbon number of homologue g = Gibbs freeenergy h = enthalpy M = number of vapor-liquid equilibrium data sets N = number of excess enthalpy data sets P = pressure

Fugacity coefficients were calculated from the Redlich-Kwong equation (1949). The temperature dependence of energy parameters in eq 2 was that used by Nagata and Yamada (1973). The molar volumes of pure components were also correlated by using a quadratic equation

A12

- A11

+ VB(l)(T) + VC(l)(T)' = x(1) X(2)(T- 273.15) + X ( 3 ) ( T - 273.15)2 +

Vi = VA(1) (7) (8)

Ai2

- A22 = X(4) + X ( 5 ) ( T - 273.15) + X ( 6 ) ( T - 273.1512

Table 111. Correlated Values of Wilson Parameters a t 25 "C Alcohol Methanol Ethanol Propanol Butanol Pentanol Methanol Ethanol Propanol Butanol Pentanol
A12

- A11

A12

(A) Alcohol-Benzene Systems 1868.09 178.10 1546.32 196.35 1346.10 205.83 1267.45 206.56 1310.36 198.52 2082.11 1745.31 1479.56 1284.84 1161.15 (B) Alcohol-Toluene Systems 167.09 186.56 202.67 215.43 224.82

- A22

Mean dev, correlated HE, cal/g-mol 2.61 4.59 5.37 6.38 12.72 4.26 5.90 5.41 5.47 4.85

Yi
0.005 0.003

0.005 0.006 0.003 0.007 0.004 0.006 0.006 0.007

Ind. Eng. Chem. Process Des. Dev., Vol. 17, No. 3, 1978 373

R = gasconstant T = absolute temperature V = molar volume VA,VB,VC = coefficients of molar volume fit with temperature
x = liquid phase mole fraction

Maripuri, V. O., Ratcliff, G. A,, J Chem. Eng. Data, 17, 366 (1972). . Mrazek. R. V.. Van Ness, H. C.. AlChEJ., 7, 190 (1961). Nagata, I., J. Chem. Eng. Data, 14, 418 (1969). Nagata. I.,Yamada, T., J. Chem. Eng. Data, 18, 87 (1973). Nielsen, R. L., Weber, J. H., J. Chem. Eng. Data, 4, 145 (1959). Orye, R. V., Prausnitz, J. M., Ind. Eng. Chem., 57 (5),18 (1965). Perry, J. H., "Chemical Engineer's Handbook", 4th McGraw-Hill, New York, N.Y.,

X(1), X(2), . . . , X ( 6 ) = coefficients of temperature dependence relationship, eq l and 8 y = vapor phase mole fraction A12, Liz1 = defined by eq 2 y = liquid phase activity coefficient X = energy term in Wilson equation @ = fugacity coefficient Subscripts cal = calculated value exp = experimental value 1 , 2 = components of binary mixture Superscripts E = excess L = liquid phase s = saturated L i t e r a t u r e Cited
Asselineau, L., Renon, H., Chem. Eng. Sci., 25, 1211 (1970). Brinkman, N. D.. Tao, L. C., Weber, J. H., Can. J. Chem. Eng., 52,(1974). Brown, I., Smith F.. Aust. J. Chem., 7, 264 (1954). Brown, I., Smith, F., Aust. J. Chem., 12, 407 (1959). Dewan, A. R., M.S. Thesis, University of Nebraska, 1976. Duran, J. L., Kaliaguine, S., Can. J. Chem. Eng., 49, 273 (1971). Fu, S.J., Lu, B. C. Y., J. Appl. Chem. (London), 16, 324 (1966). Holmes, M. J., Van Winkle, M., Ind. Eng. Chem., 62 (l), (1970). 21 Kemme, H. R., Kreps, S. I., J. Chem. Eng. Data, 14, 98 (1969). Landwehr, J. C., Yerazunis, S., Steinhauser, H. H., Chem. Eng. Data Ser., 3,231

1963.
Powell, M. J. D., Comput. J., 7, 155 (1964). Rediich, O., Kwong, J. N. S., Chem. Rev., 44, 233 (1949). Rossini, F. D., "Selected Values of Properties of Hydrocarbons & Related Compounds", A. P. I. Res. Project 44,Chemical Thermodynamic Properties Center, Texas A. & M. University, 1953. Sadler, L. Y., Luff, D. W., McKinley, M. D., J. Chem. Eng. Data, 16, 466

(1971).
Scatchard, G.,Wood, S. E., Mochel J. M., J. Am. Chem. SOC., 68, 1957

(1946).
Seetharamaswamy, V., Subrahmanyam, V., Chiranjivi, C., Dakshinamurthy, ?., J. Appl. Chem., 19 (9), 258 (1969). Shirai, H., Nakanishi, K., Kagaku Kogaku, 29 (31,180 (1965). Smith, V. C., Robinson, R. L., J. Chem. Eng. Data, 15, 391 (1970). Strubi, K., Svoboda, V., Holub, R., Collect. Czech. Chem. Commun., 37, 3522

(1972).
Timmermans, J., "Physico-Chemical Constants of Pure Organic Compounds", Elsevier Publishing Co., New York, N.Y., 1950,1965. Udovenko, V. V., Fatkulina, L. G., Zh. Fiz. Khim., 26, 719 (1952). Van Ness, H.C., Soczek, C. A., Peolquin. G. L., Machado, R. L., J. Chem. Eng. Data, 12, 217 (1967). . Vijayaraghavan, S. V., Deshpande, P. K., Kuloor, N. R., lndian J Techno/., 3 (9),

267 (1965).
Wehe, A. H., Coates, J., AlChEJ., 1, 241 (1955). Weissberger, A., Proshkanes, E. D., Reddick, T. A,, Toops E. E., "Organic Solvents", Interscience, New York, N.Y., 1955. Wilson, G. M., J. Am. Chem., SOC.,86, 127 (1964).

Department of Chemical Engineering University of Nebraska Lincoln, Nebraska 68588

Ashokkumar R. Dewan Luh C. Tao James H. Weber*

(1958).
Lu. B. C. Y., Can. J. Techno/., 34, 468 (1957).

Received for reuieu! October 11, 1977 Accepted March 8,1978

Revised Acentric Factor Values

Passut and Danner (1973) have published a set of recommended acentric factors for hydrocarbons. Revised values, based on improved extrapolation procedures, are given for a few of these acentric factors which have been found to be inconsistent.

Passut and Danner (1913) have published a set of recommended acentric factors for many hydrocarbons. These acentric factors were calculated on the basis of the best available experimental data using the exact definition of Pitzer (1955a,b). Since these values were published, some inconsistencies have been observed and further evaluations have been done for the misbehaving compounds. The compounds which were in question are listed in Table I. A review of the data indicated that the vapor pressure data for these compounds were consistent except those for 1-butyne. In addition, experimental critical properties were available for these compounds, and no reason was found to reject the critical values reported. Thus the acentric factors for these compounds were reexamined in terms of the extrapolation procedures used t o determine their vapor pressures a t a reduced temperature of 0.7. Passut and Danner had generally determined the acentric factors from the Frost-Kalkwarf (1953) equation if this value was in agreement with the values determined by interpretating (or extrapolating) the experimental data and calculated from the Antoine equation. Upon further examination of the

Table I. Recommended Acentric Factors Acentric factors PassutThis Danner work 0.0072
-

ComDound Methane 2,2,3,3-Tetramethylbutane cis- 1,3-Dimethylcyclohexane trans- 1,3-Dimethylcyclohexane cis- 1,4-Dimethylcyclohexane trans- 1,4-Dimethylcyclohexane 1-Methyl-2-ethylbenzene 1-Methyl-3-ethylbenzene 1-Methyl-4-ethylbenzene Vinylbenzene (styrene) Cyclopropane Cyclobutane 1-Butyne Propadiene

0.2237 0.1886 0.2338 0.2419 0.2937 0.3598 0.3219 0.2572 0.2645 0.2089 0.0501" 0.3125"

0.0115 0.2467 0.2414 0.2356 0.2348 0.2429 0.2941 0.3232 0.3221 0.2302 0.1279 0.1857
-

a These values appear to be in error. Because of inadequate data, however, no better values can be recommended.

0019-1882/18/1117-0313$01.00/0 0 1978 American Chemical Society