172 Wang et a\.

: Vapour-Liquid Equilibria of the Carbon Tetrachloride-Toluene System

VAPOUR-LIQUID EQUILIBRIA OF THE CARBON

TETRACHLORIDE-TOLUENE SYSTEM
By J. L. H. WANG, L. BOUBLIKOVA and B. C.-Y.LU
The vapour-liquid equilibria of the system: carbon tetrachloride-toluene were studied at five isothermal con-
ditions by use of a modified Dvorak & Boublik circulation still. Liquid activity coefficients, y, were evaluated.
The values of y were close to unity. The In y values were correlated by a threeconstant Redlich-Kister equation.

Introduction 40, 60 and 80". However, equilibrium vapour compositions

The vapour-liquid equilibria of the carbon tetrachloride- were not determined. I n this study, equilibrium T-P-x-y
toluene system have been investigated previously at atmos- values were measured at five isothermal conditions.
pheric Values reported by Ocon & Espantoso'
differ only slightly from those reported by Carey,z but the Experimental
latter differ considerably from those reported by Smit &
Research-grade toluene, supplied by Philips Petroleum
Ruyter3 and by Rodger et u I . ~From the area t e ~ t , Smit
~ . ~&
Co., and carbon tetrachloride (99.9 mole- % minimum),
Ruyter estimated that their data correspond to a heat of
supplied by Matheson, Coleman & Bell Co., were used
mixing of 110 f 60 cal/mole, while Carey's data correspond
without further purification. Physical properties of these
to a heat of mixing of 800 cal/mole. The heat of mixing materials are listed in Table I.
values recently reported by McGlashan et al.' between 8
The equilibrium still and the experimental procedure that
and 88.3" give a maximum value of only 11 cal/mole a t the
were used in this study have been described previously."
highest temperature (88.3") which is approximately the
The accuracy of the boiling temperature measurements is
average of the normal boiling points of the two pure com-
believed to be If:0.03".The accuracy of the pressure measure-
ponents. This indicates that the thermodynamic consistency
of the available isobaric data is uncertain. In order to avoid ments is consequently kO.05 mm Hg. The accuracy of the
equilibrium temperature measurements is k0.005".
the uncertainty which is caused by the temperature effect on
the liquid activity coefficients, it was decided to determine the
vapour-liquid equilibria under isothermal conditions. It
should be mentioned that Kind et ~ 1recently . ~ reported the The experimental total pressure4omposition data are
total pressure-liquid composition data for this system at presented in Table 11, and shown in Fig. 1. Liquid activity

TABLEI
Physical properties of the materials used
Refractive index at 2 5 " ~

Material Exptl. Lkg

Carbon tetrachloride (CCI,) 1.49417 1.49414
Toluene G H . ) 1.44292 144293

Vapour pressure, mm Hg

Material 35" 40" 45" 55" 65 Ref.

Exptl. Lit. Exptl. Lit. Exptl. Lit. Exptl. Lit. Exptl. Lit.
CCI, 174.4 174-38 213.3 213.23 258.8 258.86 373.3 373.42 523.6 523.78 10
CiHp, 46.8 46.75 59.2 59.15 74.1 74.13 113.4 113.46 168.8 168.76 9

Second viriil coefficient, ml/mole

Material 35" 40" 45" 55" 65"

CCI, -2148.23 -2043.8 - 1948.4 -1780.2 -1636.9
CiHs -1347.07 -1291.6 -1240.2 -1147.9 -1067.2

Liquid molal volume, ml/mole9

Material 35" 40" 45" 55" 65"

~

CCI, 98.3 98.9 99.51 100.77 102.06

C,Hs 108.02 108.62 109-24 110.47 111.73

J. appl. Chem., 1970, Vol. 20, June

 Wang et al. : Vapour-Liquid Equilibria of the Carbon Tetrachloride-Toluene System 173

coefficients were evaluated using the following equation : I 1? This equation is suitable for calculating yI values at low
pressures. The second virial coefficients of carbon tetra-
YIP + (~-P1)(B11- VI)+P6(1 -Y1Y
In y, = In -
XIPI RT RT
......(1) chloride and toluene, Bl and BZ2,were calculated according
-- . to the equation of Pitzer & Curl.13
in which The cross coefficient, B I Z ,was calculated according to the
6 = 2B12-B11-B*2 ..................... (2) method of O'Connell & Prausnitz.14 The numerical values
of the second virial coefficient together with the estimated
TABLE
I1 molal volumes of the pure components are listed in Table I.
Experimental vapour-liquid equilibrium data for the system The experimental data were correlated by means of a three-
carbon tetrachloride-toluene
constant Redlich-Kister equation :'
Temperature, Pressure,
Ycr1, In y1 = X ~ ~ [ B + C ( ~ ~ I - X ~ ) + D ( X ~ - - X ~ ) ( ~ ~ I - - Z ) I
OC mm Hg XCC14 YCCI4 calc. obs. calc. obs. In y2 = x l Z [ B + C ( x l - 3 x 2 ) + D ( x l - x 2 ) ( ~ ~ - 5 ~ ~ ) 1
35 51.9 0.0407 0. I384 1,0306 1.0268 14000 09961
55.8 0.0712 0.2247 1.0293 1.0240 1.OOO1 09950 The constants B, C and D were determined by the least-
64.4
72.5
0.1381
0.2001
0.3770
04839
1.0262
1.0231
1.0212
1.0175
1.0005 0.9938
1.0011 0.9981
squares method using an IBM 360 digital computer. The
81.4 0.2701 0.5804 1.0195 1,0140 14022 09978 constants obtained for the five temperatures are listed in
95.0 0.3762 0.6915 1.0143 1.0107 1@D46 1*oO09 Table 111. Using these constants, y values were calculated
99.4 0.411 1 0.7215 1.0127 14091 1.0057 1,0012
109.6
118.2
0.4943
05621
0.7831
0.8251
1.0092
1.0067
1.0032
14014
14086
1.0114
1.0005
1.0042
and are listed in Table 11. The values of the observed yi,
124.7 0.6145 0,8533 1.0050 0.9987 1,0138 14089 calculated by Equation (I), are also listed in Table 11. They
130.4 0.6589 04753 1.0038 0.9984 1.0159 1.0132 are all close to unity, indicating that the carbon tetrachloride-
140.1 0.7346 0.9094 1.0022 0.9985 1.0198 1.0158
147.9 0.7971 0.9342 1.0012 0.9970 1.0230 1.0182 toluene system may be considered to be nearly ideal. The
158.6 04834 0.9646 1.OOO3 0-9948 1,0275 1,0215
average deviations between the observed and the calculated
40 68.9 0.0630 0.1979 1.0318 1.0315 1. r n I 0.9964 yi values are given in Table 1V. The deviations of yi of both
80.9 0.1397 0.3724 I .0283 1.0263 j .Gj 0.9963
94.3 0.2236 03118 1.0240 1.0257 1.0014 1.OOOI
101.3 0,2731 0.5755 1.0215 1-0136 1.0022 09973
I10+3 0.3342 0,6443 1.0183 1.0132 1.0036 0.9973
1204 0.3995 0.7051 1.0151 1.0101 1.0054 0.9988
131.9 0.4719 0.7618 1.0118 14076 I ,0080 1~0010
136.1 0.4897 0.7744 1.0110 1.0087
1.0180 1.0120
141.2 0.5352 04033 14091 1,0107
1.0018 1W 4 8
144.3 0.5498 0.8 129 1.0085 1.0114
1-0082 1 ,0082
149.3 0.5731 043276 1,0076 1.0125
1.0183 1.0133
151.6 0.6059 0.8441 1.0065 1.0142
0.9972 1 ,0077
159.5 0.6428 0.8626 1.0053 1.0162
1.0097 1.0304
161.2 0.6664 0.8751 1.0046 0.9984
1.0175 1.0135
1694 0.7224 0.9011 i.&jji 0.998i 1.0209 1.0153
172.5 0.7299 0.9052 1.0029 14078 1.0214 1.0160
179.3 0.7858 0.9273 1.0018 0.9960 1,0250 14208
187.2 0.8265 0.9429 143012 1.0044 1.0278 1.0329
193.1 ,04772 0.9611 1.0006 0.9944 1.0313 1.0252
197.6 0.9032 0.9698 1 43303 0.9967 1.0332 1.0329
i97.7 04956 0.9677 1 a002 1.0035 1.0326 1.0248
81.0 0.0382 0.1238 1.0350 1.0333 1~oooO 0.9951
88.4 0.0771 0.2278 1.0334 1.0273 1~0001 0.9970
98.6 0.1317 0.3483 1,0308 1,0245 1.OOO4 09968
1128 0.2081 0.4799 1.0268 1.0204 1.0012 0,9970
122.0 0,2587 0.5498 1,0241 1.0161 1.0020 0.9965
136.8 0.3396 0.6421 i.oi97 1.0121 1.0039 0.9962
147.5 0.3982 0.6971 1.0165 1.0092 1.0057 0.9970
157.1 0.4502 0.7395 1.0139 1.0076 1.0076 0.9990
165.8 0.4973 0.7739 1.0117 1.0065 14096 1.0003
178.9 0.5715 0.8198 1.0084 0.9997 1.0133 1.0084
188.6 0.6254 0.8497 1.0064 0.9972 1.0164 1.0136 x,y, mole fraction CCl'
1964 0.6689 0.87211 1.0049 0.9985 1.0191 1.0123
208.0 0.jjji 0.9bc i.0032 0.9956 1.0233 i . o i a
218.2 0.7869 0.9256 14020 0.9958 1.0272 1.0186 Fig. 1. Total vapour pressure-composition diagram for the carbon
232.3 04679 0.9563 1.0007 0.9916 1.0333 1,0267 tetrachloride-toluene system at jive isothermal conditions
132.8 0.0767 0.2173 1.0386 1.0307 1@004 09914 (a) 65"; (b) 55"; (c) 45"; (d) 40";(e) 35"
142.4 0.1117 0.2949 1.0345 1,0290 1@008 09949
153.2 0.1518 0.3716 1.0304 1.0254 1QO14 0.9983 TABLE111
168.6 0.2122 04696 1.0253 1,0187 1,0025 0.9976
.__ . . .... . Constants of the Redlicb-Kister equation
195.6 0.3175 0.6037 1.0187 0.9966
215.9 0.3967 0.6818 1.0150 1.0068 0.9981
234.1 04672 0-7399 1.0123 1 9089 1 4006 Temperature, O c B C D
2524 0-5423 0.7924 1.0098 1,0114 1.0029
270.5 0.611 I 0.8341 1 4077 1.0143 1.0083 35 0.0353 04003 -0.0033
285.9
-..
302.5
0.6721
0.737i
0.8676 1 .O060 1.0175
0.8991 i.0042 0.9949 1.0217
1.0079
1,0127 40 0.0392 0.0028 - 0.0027
318.9 0.7978 0.9259 1,0028 0,9964 1.0267 1.0186 45 0.0424 0.0035 -0.0031
330.7 0.8422 0-9439 1.0018 0.9968 1.0312 1,0240 55 0.0420 0.0025 04089
348.3 0.9099 0.9692 1.0007 0.9961 1,0396 1.0360
65 0.0413 0.0031 0.0048
65 184.8 0.0489 0.1386 1.0386 1.0301 l~OoO1 0.9905
195.4 0.0782 0.2090 1.0357 1.0261 1.0003 0.9918
220.6 .. -l d X 1 0.3498
O I . o m 1,0202 1.0011 0.9948 TABLEIV
241.3 0.2081 0.4475 i .0%4 1.0155 1 .0020 0.9934
264.0 0.2732 0.5359 1,0214 1.0116 1,0032 09935 Average deviation of y values, %
296.4 0.3646 0.6372 1.0167 1 4 0 9 1 1 43054 0.9957
325.9 04487 0.7122 1.0131 1 @052 1 4078 0.9995
342.3 0.4959 0.7492 1.0113 1 a 3 5 1.0094 0.9997 Temperature, 'c Carbon tetrachloride Toluene
360.8 0.5491 0-7853 1 4094 09998 1.0115 1.0075
391.3 0.6362 0.8402 1,0066 0.9987 1.0156 1 43064 35 0.48 0.49
405.6 0.6761 0.8621 1.0054 09984 1.0179 1.0104 0.50
423.2 0.iiii 04864 1.0041 0.9984 1.0209 1.0170 40 0-49 . _.
448.1 0.7947 0.9199 1.0025 0.9978 1.0263 i .OioS 45 0.68 0.62
461.2 0,8306 0.9356 14OI8 0.9982 1.0295 1.0231 55 0-69 0.71
475.1 0,8753 0.9538 1~0010 09936 1.0341 1 :0264
485.4 0.9054 0.9655 1.0006 0.9926 1,0375 1.0317 65 0.78 0.73

J. appl. Chem., 1970, Vol. 20, June

174 Wang et al. : Vapour-Liquid Equilibria of the Carbon TetrachloriBe-Toluene System
components increase as temperature increases. It may also be References
mentioned that the measured P- x data of this investigation &on, J., & Espantoso, J., An. R. SOC.esp. Fis. Quim., 19589
agree well with those reported by Kind et a/.* 54B,421
Carey, J. S., Sc.D. Thesis, Mass. Inst. Technol., 1930; data
Nomenclature compiled by Chu, J. C., ‘Distillation equilibrium data’, 1950
(New York: Reinhold Publishing Co.)
B,C. D constants in Redlich-Kister equation Smit, W. M.,& Ruyter, J. H., Reel Trav. chim. Pays-Bas Belg.,
B1 I , B 2 2 second virial coefficient of pure components 1 and 1960,79, 1244
2, respectively Rodger, A. J., Hsu, C. C., & Furter, W. F., J. chem. Engng Data,
B12 cross coefficient 1969,14, 362
P Redlich, O., & Kister, A. T., Ind. Ensng Chem., 1948, 40,345
total pressure Coulson, E. A,, & Herrington, E. F. G., Trans. Farodoy SOC.,
P vapour pressure of pure component 1948,44, 629
R gas constant McGlashan, M. L., Stubley, D., &Watts, H., J. chem. Soc., A ,
T absolute temperature 1969, p. 673
Kind, R., Kahnt, G., Schmidt, D., Schumann, J., & Bittrich,
V liquid molal volume of pure component H. J., 2.phys. Chem., 1968,238, 277
X liquid mole fraction Driesback, R.R.,‘Physical properties of chemical substances’,
Y vapour mole fraction 1953 (Midland, Mich.: Dow Chemical Co.)
Y liquid activity coefficient lo Barker, J. A., Brown, I., & Smith, F., Discuss. Faraday SOC.,
6 defined in Equation (2) 1953,15, 142
Boublikova, L., & Lu, B. C.-Y., J. appl. Chem., Lond., 1969,19,
subscripts 89
l2 Van Ness, N. C., ‘Classical thermodynamics of non-electrolyte
1,2, i, ii components solutions’, 1964 (New York: Macmillan Co.)
l3 Pitzer, K. S., & Curl, R. F., jun., J. Am. chem. SOC., 1957, 79,
2369
Acknowledgment OConnell, J. P., & Prausnitz, J. M., Inn. Engng Chem. Process
The authors wish to thank the National Research Council Des. Dev., 1967, 6, 245
of Canada for financial support.
Department of Chemical Engineering,
University of Ottawa,
Ottawa,
Ontario, Canada
Received 3 November, 1969;
amended manuscript 9 February, 1970

J. appl. Chem., 1970, Vol. 20, June