J. Chem.

i%ermodynamics 1976,8, 127-131

Activity n-alkane

coefficients mixtures

of cyclohexane

T. M. LETCHER

and P. JERMAN

Departmentof Chemistry, University of the Witwatersrand, Jan SmutsAvenue,Johannesburg, South Africa (Received21 July 1975)
The activity coefficients of cyclohexane at infinite dilution in the solvents n-hexadecane, n-octadecane, n-eicosane, n-tetracosane, n-octacosane, and n-dotriacontane have been determined at various temperatures using g.1.c. These results together with tiite-concentration activity coefficients from the literature of cyclohexane + n-octane, + n-dodecane, + n-hexadecane, and + n-eicosane were analysed in terms of the Guggenheim-MillerFlory-Huggins one-parameter equation and also fitted to a simple three-parameter segment model of the lattice theory. The result is one equation which can be used for predicting activity coefficients for cyclohexane + n-alkane in the range C8 to Csa over a 50 K temperature range to within 2 per cent.

1. Introduction The Guggenheim-Miller-Flory-Huggins (GMFH) equation() and the threeparameter segment model of the lattice theoryc2 3, together have been successful in fitting the activity coefficients of benzene + an n-alkane.(4) Here these equations have been applied to the activity coefficients of cyclohexane + an n-alkane. The activity coefficients at finite concentrations were obtained from the literature but the activity coefficients at infinite dilution were measured using g.1.c. and are presented here. 2. Experimental The g.1.c. apparatus used to determine the activity coefficients at infinite dilution has been described.(3 The column specifications are given in table 1.
TABLE, 1. Column specifications. In all cases copper tubing of 2 m length and 4.2 mm bore was used, m3denotes the mass of solvent on the column, e the percentage loading, and n3 the amount of solvent on the column Solvent n-hexadecane n-octadecane n-eicosane n-tetracosane n-octacosane n-dotriacontane mdg 1.3900 0.4600 1.2076 0.9114 1.6340 1.7038 e 7.12 4.91 11.92 6.47 13.15 15.23
iZ&ltllOl

6.138 1.808 4.274 2.691 4.139 3.779

128

T. M.

LETCHER

AND

P. JERMAN

The stationary phases, n-octadecane, n-eicosane, n-tetracosane, n-octacosane, and n-dotriacontane, were supplied by Aldrich Chemical Company and n-hexadecane by B.D.H. In all cases the quoted purity was better than 98 moles per cent and the alkanes were used without further purification. The celite (SO/l00 mesh) was supplied by B.D.H. as was the cyclohexane. The solvents used in this work were chosen by their convenient melting temperatures (in the range 290 K to 340 K).

The retention volumes were determined from peak half-areasc5 rather than from peak tangents@ or peak averages. t3) This gives a better approximation to peak maximum.(5) All columns were tested for homogeneity in packing at least once,
TABLE 2. The parameters a and b of the equation log,,(V,/m) = a - b(p,J?) together with the results for log,,yz and the mixed second virial coefficient (cyclohexane + nitrogen) &!A. Also included are values of x, the standard deviation c of the straight-line fit, and the difference between calculated (segment model) and experimental values of y b GPa-1

-a

10% n-hexadecane 19 0.1013 28 0.1163 13 0.1209 30 0.1296 n-octadecane 36 0.1278 16 0.1337 9 0.1379 28 0.1475 27 20 18 22 n-eicosane 0.1599 0.1656 0.1669 0.1752

Iy%

Y%l

298.15 313.15 323.15 333.15 308.15 313.15 323.15 333.15 313.15 318.15 323.15 333.15 328.15 333.15 343.15 348.15 338.15 343.15 348.15 353.15 343.15 348.15 353.15

2.8263 3.0643 3.2112 3.3422 3.5029 3.5771 3.7251 3.8551 3.1779 3.2496 3.3425 3.4538 3.5643 3.6286 3.7510 3.8074 3.4780 3.5378 3.5949 3.6493 3.5371 3.5943 3.6484

64.11 56.02 52.61 49.19 60.28 55.87 52.99 49.20 55.89 54.15 52.46 49.71 50.73 48.84 46.33 44.67 47.53 46.10 44.25 42.79 45.84 44,49 43.55

129 113 106 100 123 112 107 100 112 109 106 102 103 99 95 91 97 94 90 87 93 91 89

0.132 0.094 0.081 0.059 0.136 0.122 0.109 0.084 0.126 0.111 0.107 0.084 0.154 0.143 0.125 0.114 0.181 0.172 0.162 0.152 0.177 0.168 0.156

0.0035 0.0040 0.0023 0.0074 0.0037 0.0021 0.0056 0.0001 0.0088 0.0081 0.0089 0.0097 0.0047 0.0039 0.0045 0;0030 0.0029 0.0035 0.0034 0.0032 0.0004 0.0010 0.0009

n-tetracosane 17 0.1972 13 0.2013 15 0.2076 19 0.2118 n-octacosane 25 0.2306 28 0.2338 31 0.2373 22 0.2411 n-dotriacontane 42 0.2741 31 0.2774 27 0.2815

ACTIVITY

COEFFICIENTS

OF CYCLOHEXANE

+ n-ALKANE

129

by determining the retention volume in both the forward and reverse directions. In no case was a significant difference noticed. The columns were continually checked by using solutes such as benzene and hexane for which accurate activity coefficients are known. The activity coefficients yyS were calculated as before.() The vapour pressure pT of cyclohexane over the temperature range of 290 K to 350 K was determined from the equation:@)t log,,(pT/Torr) = 6.8413 - 1201.531/( -50.503 + T/K). (1) The temperature dependence of the molar volumes V:,(*) and the second virial coefficients B, ], c9) of cyclohexane were fitted to the equations: VT(T)/cm3 mole1 = 66.542+0.1414(T/K); (o/cm3 mole1 = 0.06), (2)
and

(a/cm3 mol-l = 6). (3) The activity coefficients are given in table 2 and are estimated to have an uncertainty of kO.003 in log,,y~3.
B,,(T)/cm3 mol-l

= -9935.3+42.06(T/K)-O.O5(T/K);

4. Discussion
INTERACTION eicosane) PARAMETER 2

The finite-concentration activity coefficients for cyclohexane + n-alkane (octane to were fitted to the GMFH equation:

In 73 = W - hdx~ +(I - VWh +x422, (4) where & is the volume fraction of the alkane, x1 the mole fraction of benzene, and x the interaction parameter. We have again chosen r to be the ratio (VJV,) of the
TABLE 3. Results of (a) fitting the GMFH equation to literature values of finite-concentration activity coefficients y, and (b) testing the segment model results of y against the experimental values. The estimated experimental deviations in y are all about 0.004 Alkane Ref. 14 298.15 308.15 318.15 328.15 298.02 305.04 312.48 298.02 305.04 312.48 305.94 312.64 317.40 x from GMFH 0.149 0.136 0.126 0.111 0.119 0.102 0.091 0.132 0.119 0.100 0.139 0.126 0.114
CT

GMFH equation 0.002 0.002 0.001 0.001 0.002 0.001 0.001 0.002 0.006 0.003 0.006 0.005 0.008

Segment model 0.004 0.002 0.002 0.002 0.008 0.003 0.004 0.002 0.008 0.002 0.011 0.010 0.015

CJ&s

G&L,

15

Cd%4

16

G&z

17

t Throughout

this paper Torr = (101.325/760) kPa.

130

T. M. LETCHBR

AND P. JERMAN

volumes of molecules.(4) The values of V, and V, were obtained or extrapolated from values given in the literature.@ The values of x which gave the best fit are given in table 3, together with their standard deviations Q. All the reliable y results found in the literature were used in this study. The cyclohexane + hexane,(loP I) and cyclohexane + heptane,( 13) results are not included in this work because their results do not fit on a smooth curve with the other results. It is possible that the segment model used in this work is applicable only to mixtures with the higher alkanes. At infinite dilution equation (4) becomes: In $ = In(l/r)+(l The x values determined
SEGMENT MODEL

-l/r)+x.

(5)

from the infinite dilution

results are given in table 2.

In order to fit the experimentally determined x values to the segment model(2P 3, over a 50 K temperature range, the experimental values of x and temperature were fitted analytically. The results are given in table 4.
TABLE 4. The parameters c and d of equation x = c + d(Z,,K - 273.15) and the standard deviation o, obtained from the data of tables 2 and 3 for various cyclohexane + n-alkane mixtures. The carbon number of the n-alkane is represented by n c 0.5116 0.1648 0.1832 0.2039 0.2049 0.2609 0.3084 0.3212 -103d 1.22 1.91 2.09 1.97 2.01 1.95 1.95 2.06 10% 1.1 1.7 2.8 3.2 1.8 0.91 0.57 0.56

The segment model considered here involves three segments: (-CH,-) or A type, (-CH,) or B type and one-sixth cyclohexane (-CH,-) or C type, and thus involves the identical three-parameter equation used in the benzene -I- n-alkane work.) The equation : (6) + {7/(n + 5)1% + {(n -2Mn + 5))c~, defines x in terms of segment interchange energies (o,~, cc,,, and c.& and an adjustable parameter m, which relates C type segments to C type units.(4) The x values (from table 4) at six temperatures (ranging in 10 K intervals between 293.15 K and 343.15 IS) were fitted to wao obO, and m, as before.c4) The values of o,, and wbcfor the average value of m, (found to be 3.105) together with the literature values of o,, (for mb = 3.50) are given in table 5.

kTx/6m; = - 7{(n - 2)/(n + 5))~,

ACTIVITY TABLE

COEFFICIENTS

OF CYCLOHEXANE

+ n-ALKANE over the range of

131

5. The parameters a and b of equation (w/k) = e +f(T,K) temperature 293.15 to 343.15 K

20.156 25.965 67.185

0.036 0.030 0.070

0.031 0.003

The segment-model equation together with the GMFH equation reproduces the experimentally determined activity coefficients to within twice the experimental errors of the experimental values as can be seen in the final columns of tables 2 and 3. Thus, equations (4) and (6) or (5) and (6) reproduce the experimental activity coefficients to within 2 per cent. The authors wish to thank the C.S.I.R. (S. Africa) for financial aid.
REFERENCES 1. Ashworth, A. J.; Everett, D. H. Trans. Fur&y Sot. 1960, 56, 1609. 2. Cruickshank, A. J. B.; Gainey, B. W.; Hicks, C. P.; Letcher, T. M.; Young, C. L. Trans. Faraday Sot. 1969,65,2356. 3. L&her, T. M.; Marsicano, F., J. Chem. Thermodynamics 1974, 6, 501. 4. Letcher, T. M. J. Chem. Thermodynamics 1975, 7, 969. 5. Buffham, B. A. Proc. Roy. Sot. 1973, A333, 89. 6. Cruickshank, A. J. B.; Windsor, M. I.; Young, C. L. Proc. Roy. Sot. 1966, A295, 271. 7. Letcher, T. M.; Netherton, G. J. Chem. l?zermodynamics 1975, 7, 353. 8. Selected Values of Properties of Hydrocarbon and Related Compounds. American Petroleum Institute, Research Project 44, Thermodynamics Research Centre. Texas A & M University, College Station, Texas. 1970. 9. Dymond, J. H.; Smith, E. B. The Virial Coeficients of Gases. Clarendon Press, Oxford. 1969. 10. Butler, P. A.; Ridgway, K. J. Appl. Chem. 1967, 17, 191. 11. Li, I. P.-C.; Lu, B. C-Y. J. Chem. Eng. Data 1973,16,305. 12. Crutzen, von J. L.; Haase, R.; Seig, L. Z. Nuturfirschg. 1950, 5a, 600. 13. Katayama, T. ; Sung, E. K.; Lightfoot, E. N. AZChE J. 1965, 11, 924. 14. Jain, D. V. S.; Vadav, 0. P. Indian J. Chem. 1971, 9, 342, 1.5. Gbmez-Ib&ez, J. D.; Shieh, J. J. C.; Thorsteinson, E. M. J. Phys. Chem. 1966, 70, 1998. 16. Gbmez-Ibtiez, J. D. ; Shieh, J. J. C. J. Phys. Chem. 1965, 69, 1660. 17. Gbmez-Ib&ez, J. D.; Wang, F. T. J. Chem. Thermodynamics 1971, 3, 811.