Fluid Phase Equilibria, 58 (1990) 319-324 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

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EXCESS VOLUMES FOR BINARY LIQUID MIXTURES OF 1,4- DIOXANE WITH METHYLENE CHLORIDE, l,Z-DICHLOROETHANE, TRICHLOROETHYLENE, TETRACHLOROETHYLENE AND CYCLOHEXANE AT VARIOUS TEMPERATURES

JAGAN NATH * and RASHMI

Chemistry Department, Gorakhpur University, Gorakhpur-273009 (India)

(Received June 27,1989; accepted in final form January 18,199O)

ABSTRACT

Nath, J. and Rashmi, 1990. Excess volumes for binary liquid mixtures of 1,4-dioxane with methylene chloride, 1,2-dichloroethane, trichloroethylene, tetrachloroethylene and cyclohexane at various temperatures. Fluid Phase Equilibria, 58: 319-324.

Dilatometric measurements of excess volumes, VE, have been made for l,Cdioxane+ methylcne chloride (CH,Cl,) and l,+dioxane t 1,2-dichforoethane (CH,CICH,Cl) at 293.15 and 303.15 K, for l+dioxane + trichloroethylene (CHClCCl,) and 1,4-dioxane + tetrachloroethylene (CCI,CCI,) at 298.15 and 308.15 K and for l+dioxane+cyclohexane (c-C,H,,) at 303.15 K. The values of VE have been found to be positive for l,Cdioxane+c- CsH,,, 1,4_dioxane+CCl,CCl, and l&dioxane t CH,CICH,Cl. Some negative values of VE have been found for 1,4_dioxane+CHClCCl, and l&dioxane t CH&l,. The results indicate the possible existence of specific interaction of 1,Cdioxane with CH,Cl,, CHClCCl,, CH,ClCH,Cl and CCl,CCl,.

INTRODUCTION

Binary systems of 1,4-dioxane with methylene chloride (CH,Cl,), 1,2-di- chloroethane (CH,ClCH,Cl), trichloroethylene (CHClCCl,), tetrachloroeth- ylene (CCl,CCl,) and cyclohexane (c-C,H,,) are of considerable interest from the viewpoint of the existence of specific interaction between the components. Due to the presence of Cl and H atoms in CH,Cl,, CH,ClCH,Cl and CHClCCl,, these compounds can act as u-acceptors towards, and be involved in the formation of hydrogen bonds with, 1,4-d&

oxane which can act as an n-donor. In addition, CCl,CCl, can act as a u-acceptor towards 1,4-dioxane. The system 1,4-dioxane + C-C,H,,, in which only non-specific forces between the components are believed to be present, can be used as a reference system (Nath and Dixit, 1985; Nath and Singh,

* Author to whom correspondence should be addressed.

0378-3812/90/$03.50 0 1990 - Elsevier Science Publishers B.V.

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1987). Excess volumes, VE, have previously been measured for binary systems of 1,Cdioxane with 1,Zdichloroethane (Vij and Mahl, 1975) and cyclohexane (Andrews and Morcom, 1971; Deshpande and Oswal, 1975; Suri and Ramakrishna, 1969; Mato and Femandez-Polanco, 1974), but no studies of binary systems of 1,4-dioxane with chloroalkanes and chloroal- kenes of varying molecular complexity have been made. Hence, in the present programme, we have measured VE for binary liquid mixtures of 1,4-dioxane with CH,Cl,, CH,ClCH,CI, CHClCCl,, CCl,CCl, and c-C,H,, at different temperatures, and the results obtained are discussed here.

EXPERIMENTAL

1,2-Dichloroethane (SRL, A.R.) was washed with an aqueous solution of sodium hydrogen carbonate, dried over anhydrous calcium chloride and distilled over phosphorus pentoxide. Trichloroethylene (SRL, A.R.) was shaken with a solution of potassium carbonate, washed with water, dried over anhydrous potassium carbonate and calcium chloride, and then sub- jected to fractional distillations. Cyclohexane (Merck, Darmstadt, F.R.G.), tetrachloroethylene (Merck, Darmstadt, F.R.G.) and methylene chloride (SRL), all spectral grade chemicals, were dried over anhydrous calcium chloride prior to use. Spectral grade 1,4-dioxane (SRL) was stored over sodium wire. The refractive indices of CH,ClCH,Cl, CHClCCl,, C-C,H,,, CC1,CC12 and 1,6dioxane were measured at 308.15 K with an accuracy of +0.0002, and were found to be 1.4370, 1.4694, 1.4182, 1.4978 and 1.4155, respectively. These values are in good agreement with the literature (Timmermans, 1950; Riddick and Bunger, 1970) values 1.43725, 1.46948, 1.41814, 1.49771 and 1.41578, respectively. The refractive index of CH,Cl, measured at 303.15 K was 1.4182, in agreement with the literature (Riddick and Bunger, 1970) value 1.41840.

Excess volumes, VE, with a precision of the order of f0.002 cm3 mol-‘, were measured using a two-limbed dilatometer which was similar to that used in earlier measurements (Nath and Dubey, 1979; Nath and Singh, 1986). The dilatometer (mounted on a stand) was immersed in a thermo- statted bath which was maintained at the required temperature (controlled to +O.Ol K). The uncertainty in the mole fractions of the components in various mixtures is of the order of f0.0002. The mercury levels in the capillary of the dilatometer were noted using a cathetometer which could read correct to fO.OO1 cm.

RESULTS AND DISCUSSION

The experimental values of VE for the systems 1,4-dioxane with CHQ,, CH,ClCH,Cl, CHClCCl,, CCl,CCl, and I&H,, at various temperatures

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are given in Table 1, and have been fitted by a least-squares method to the equation

V”=XIXZIAO+Al( x1 - x2) + A*(+ - %,‘] (1)

where x, is the mole fraction of 1,4-dioxane, x2 is the mole fraction of the

TABLE 1

Experimental values of excess volumes, V E, for binary liquid mixtures of 1,Cdioxane with CH,CI,, CH,ClCH,Cl, CCl,CCl,, CHCICCI, and c-C,H,, at various temperatures

x1 VE x1 VE Xl VE X1 VE (cm3 mol-‘) (cm3 mol-‘) (cm3 mol - ’ ) (cm3 mol-‘)

1,4-Dioxane+ CH,Cl, 293.15 K 303.15 K 0.0965 - 0.015 0.0336 - 0.009 0.1763 - 0.019 0.0865 - 0.026 0.2349 - 0.023 0.1257 -0.033 0.3051 -0.017 0.1356 -0.039 0.4158 0.005 0.3408 -0.038 0.4832 0.020 0.3782 - 0.034 0.5030 0.020 0.4313 - 0.027 0.6171 0.044 0.4776 -0.018 0.6512 0.055 0.5357 -0.006 0.7151 0.063 0.6331 0.010 0.7436 0.061 0.7122 0.020 0.7877 0.058 0.8195 0.029

0.8637 0.027 0.9477 0.011

1,4-Dioxane+CH,ClCH,CI 293.15 K 303.15 K 0.1041 0.065 0.0534 0.033 0.1362 0.085 0.1613 0.091 0.2141 0.131 0.2186 0.115 0.2530 0.153 0.2400 0.126 0.2643 0.155 0.3129 0.157 0.3044 0.174 0.3832 0.172 0.4327 0.215 0.4333 0.180 0.4949 0.231 0.4774 0.188 0.5383 0.234 0.5260 0.193 0.5392 0.229 0.6598 0.178 0.6357 0.228 0.6789 0.178 0.7389 0.198 0.7149 0.164 0.7398 0.197 0.7680 0.149 0.9143 0.089 0.8070 0.130

0.9243 0.058

1,4-Dioxane+CHClCC& l,CDioxane+CCl,CCl, 298.15 K 308.15 K 298.15 K 308.15 K 0.1022 - 0.041 0.0618 -0.032 0.0947 0.105 0.0887 0.112 0.1081 - 0.046 0.0842 - 0.043 0.1233 0.130 0.1331 0.155 0.1681 - 0.054 0.2326 - 0.062 0.2110 0.199 0.2934 0.264 0.2855 - 0.046 0.2356 -0.057 0.3172 0.257 0.3508 0.290 0.3377 -0.039 0.3447 - 0.041 0.3611 0.270 0.4439 0.309 0.4008 - 0.023 0.4024 -0.026 0.3900 0.279 0.5039 0.313 0.4176 - 0.016 0.4580 - 0.009 0.4898 0.297 0.5396 0.313 0.5200 0.012 0.5202 0.012 0.5564 0.296 0.5866 0.309 0.6187 0.042 0.5634 0.026 0.5899 0.286 0.6420 0.291 0.6619 0.053 0.6552 0.047 0.6330 0.278 0.6762 0.282 0.7510 0.066 0.7170 0.060 0.6853 0.255 0.8157 0.204 0.8084 0.065 0.9148 0.046 0.7834 0.206 0.8511 0.172 0.8792 0.053 0.9272 0.041 0.8252 0.177 0.9177 0.041 0.9118 0.103

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TABLE 1 (continued)

XI VE (cd mol-‘)

l&Dioxane + c-CsHI, 303.15 K 0.1015 0.420 0.1635 0.606 0.1844 0.660 0.2172 0.131 0.3664 0.925 0.4015 0.943 0.5153 0.933 0.6105 0.855 0.7564 0.648 0.8656 0.402 0.9182 0.254 0.9571 0.141

other component in each system, and A,, A, and A, are constants char- acteristic of a system at a given temperature. The values of these constants, along with the standard deviations, S( V”), for the various systems are given in Table 2. The values of VE for each system at one temperature have been plotted against the mole fraction x1 of 1,Cdioxane in Fig. 1.

The data show that the values of VE are positive throughout the whole range of composition for the systems 1,4-dioxane with C-C,H,,, CCl,CCl, and CH,ClCH,Cl, but for the systems 1,Cdioxane with CHClCCl, and CH,Cl,, YE has been found to be slightly negative at low mole fractions of

TABLE 2

Values of the constants A,, A, and A, of eqn. (1) and the standard deviations s(ve) for the various systems of l&dioxane

system Temp. A, Al Al WEI (K) (cm’ mol-‘) (ems mol-‘) (cm3 mol-‘) (cm3 mol-‘)

1,4Dioxane+CH,Cl, 293.15 0.0844 0.4267 0.1200 0.0032 303.15 -0.0581 0.3355 0.0340 0.0029

1,4-Dioxane+ CH,ClCH,Cl 293.15 0.9164 0.2531 - 0.0060 0.0023 303.15 0.7625 0.1175 - 0.0212 0.0021

1,4-Dioxane+ CHCICCI, 298.15 0.0328 0.6224 - 0.0061 0.0015 308.15 0.0171 0.6725 0.0126 0.0022

1,4-Dioxane + CCl,CCl s 298.15 1.1777 0.0268 0.0965 0.0023 308.15 1.2544 0.0178 0.2031 0.0018

1,4-Dioxane+ C-GH,, 303.15 3.7622 - 0.7409 0.4014 0.0031

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1.00

0.80

_:1”‘\1

0.60

i % E o?_O

3 5

0.00

/ I I 0.0 02 on 06 08 I.0

Xl

Fig. 1. Plot of VE against mole fraction of 1,4-dioxane, x,, for the various systems: l , 1,4-dioxane+c-C,H,, at 303.15 K; V, 1,Qdioxane + CCl,CCl, at 298.15 K; 8, l+dioxane + CH,ClCH,Cl at 303.15 K; a, l+dioxane+CHClCCl, at 298.15 K; 0, l,Cdioxane+CH,Cl, at 303.15 K.

1,4dioxane and slightly positive at high mole fractions. The negative values of VE for the systems 1,4-dioxane with CHClCCl, and CH,Cl, indicate the possible existence of specific interaction of 1,Cdioxane with CHClCCl, and CH,Cl, in the liquid state. The values of VE which are slightly positive for the systems 1,4-dioxane with CH,ClCH,Cl and CCl,CCl,, compared with VE values for l&dioxane and C-C,H,,, also indicate the possible existence of specific interaction of 1,4-dioxane with CH,ClCH,Cl and CCl,CCl,. The data show that the values of the temperature coefficient (WE/U), are positive for 1,Cdioxane t CCl,CCl, and negative for 1,Cdioxane + CH,Cl, and 1,6dioxane + CH,ClCH,Cl. However, VE is found to be independent of temperature in the case of 1,6dioxane + CHClCCl,. Positive values of (avE/azy, for 1,4-d* ioxane + CCl,CCl, indicate specific interaction of 1,4-dioxane with CCl,CCl,, whereas the negative values of (WE/U), for the systems 1,Cdioxane with CH,Cl, and CH,ClCH,Cl can be seen to be due to the predominance of contributions to VE from dipolar forces over those from specific interaction. It should, however, be pointed out that

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independent measurements of excess Gibbs free energies GE and excess enthalpies HE for the various systems are needed to give conclusive evi- dence in support of our view concerning the existence of specific interaction between the components.

ACKNOWLEDGEMENTS

We are extremely grateful to Professor S. Giri, Head of the Chemistry Department, Gorakhpur University, Gorakhpur, for providing laboratory facilities. Thanks are also due to the Council of Scientific and Industrial Research, New Delhi, India, for financial support.

REFERENCES

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Deshpande, D.D. and Oswal, S.L., 1975. Thermodynamics of mixtures containing p-dioxan or tetrahydrofuran 1. Excess Gibbs free energies and excess volumes. J. Chem. Therm@ dyn., 7: 155-159.

Mato, F. and Fernandez-Polanco, F., 1974. Dielectric properties of liquid mixtures. I. Nonpolar-nonpolar and polar-polar systems. An. Quim., 70: 76-81.

Nath, J. and Dixit, A.P., 1985. Binary systems of acetone with tetrachloroethylene, trichloro- ethylene, methylene chloride, 1,2_dichloroethene and cyclohexane. Part 3 - Dielectric properties and refractive indices at 303.15 K. J. Chem. Sot. Faraday Trans. 2, 81: 11-19.

Nath, J. and Dubey, S.N., 1979. Excess volumes for trichlorocthylene+ benzene, t toluene, +p-xylene, + tetrachloromethane, and + trichloromethane at 303.15 K. J. Chem. Thermo- dyn., 11: 1163-1165.

Nath, J. and Sir@, G., 1986. Excess volumes for binary liquid mixtures of 1,2_dichloroethane with benzene, toluene, p-xylene, quinoline and cyclohexane. J. Chem. Eng. Data, 31: 115-116.

Nath, J. and Sit@, G., 1987. Binary systems of 1,2-dichloroethane with benzene, toluene, p-xylene, quinoline and cyclohexane. Part 3 - Dielectric properties and refractive indices at 308.15 K. J. Chem. Sot. Faraday Trans. 1, 83: 3167-3175.

Riddick, J.A. and Bunger, W.B., 1970. Techniques of Chemistry. Vol. II, Organic Solvents: Physical Properties and Methods of Purification, 3rd Edn., Wiley, New York.

Suri, S.K. and Ramakrishna, V., 1969. Volume of mixing of some binary solutions. Indian J. Chem., 7: 490-494.

Timmermans, J., 1950. Physicochemical Constants of Pure Organic Compounds. Elsevier, Amsterdam.

Vij, J.N. and Mahl, B.S., 1975. Thermodynamics of binary mixtures. Excess volumes of mixing of some 1,2-dichloroethane mixtures. Thermochim. Acta, 12: 1555158.