Fluid Phase Equilibria, 50 (1989) 297-303 Elsevier Science Publishers B.V.. Amsterdam - Printed in The Netherlands

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EXCESS VOLUMES FOR BINARY LIQUID MIXTURES OF METHYLETHYLKETONE WITH METHYLENE CHLORIDE, l,ZDICHLOROETHANE, TRICHLOROETHYLENE, TETRACHLOROETHYLENE AND CYCLOHEXANE AT VARIOUS TEMPERATURES

JAGAN NATH and RENU SAINI

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

(Received March 2, 1989; accepted in final form May 18, 1989)

ABSTRACT

Nath, J. and Saini, R., 1989. Excess volumes for binary liquid mixtures of methylethylketone with methylene chloride, 1,2-dichloroethane, trichloroethylene, tetrachloroethylene and cyclohexane at various temperatures, Fluid Phase Equilibria, 50: 297-303.

Dilatometric measurements of excess volumes V E have been made for binary liquid mixtures of methylethylketone with methylene chloride (CH ,C12), 1,2-dichloroethane (CH,ClCH,Cl) and tetrachloroethylene (CCl,CCl,) at 293.15 and 303.15 K, for mixtures of methylethylketone with trichloroethylene (CHClCCl,) at 298.15 and 308.15 K, and for mixtures of methylethylketone with cyclohexane (c-C,H,,) at 303.15 K. The values of I” have been found to be highly positive for methylethylketone-t C-C,H,,, slightly positive for methylethylketone + CH ,Cl 2 and methylethylketone + CC1 &Cl *, and slightly negative for methylethylketone + CHClCCl 2 and methylethylketone + CH ,ClCH ,Cl. The results indicate the existence of specific interactions of methylethylketone with CH,Cl z, CH ,ClCH ,Cl, CHClCCl, and CC1 &Cl *.

Recently, Nath and Dixit (1984a,b, 1985) have made measurements of excess volumes, ultrasonic velocities, dielectric properties and viscosities of binary systems of acetone (dimethylketone) with methylene chloride (CH,Cl,), 1,2-dichloroethane (CH,ClCH,Cl), trichloroethylene (CHCl- CC1 2), tetrachloroethylene (CC1 &Cl 2) and cyclohexane (c-C,H,,) at vari- ous temperatures, and it has been pointed out that there exist specific interactions between acetone and these chloro-compounds. However, exten- sive studies concerning interactions of chloroalkanes and chloroalkenes with ketones of varying molecular complexity have not been carried out previ- ously, and the binary systems of methylethylketone with CH,Cl 2, CH,Cl- CH,Cl, CHClCCl,, CCl,CCl, are of considerable interest from the above

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viewpoint. The system methylethylketone + C-CgH12, in which case non- specific interactions are believed to be present between the components, is of interest as it will serve as a reference system (Nath and Singh, 1987). Hence, in the present programme, we have measured excess volumes VE for binary mixtures of methylethylketone with CH ,Cl 2, CH ,ClCH,Cl, CHCl- Ccl,, CCl,CCl, and C-CgH12, and the results obtained are discussed here.

Cyclohexane (BDH) of reagent grade was purified by the method de- scribed by Adcock and McGlashan (1954), and 1,2-dichloroethane (BDH) was purified as described by Foster and Fyfe (1966). Spectral grade tetra- chloroethylene (E. Merck, Darmstadt) and methylene chloride (E. Merck, Darmstadt) of guaranteed reagent quality were placed over anhydrous calcium chloride and distilled. Trichloroethylene (SRL) of analytic reagent quality was shaken with potassium carbonate solution, washed several times with water, dried over anhydrous potassium carbonate and calcium chloride, and then fractionally distilled. Methylethylketone (SRL) of analytical re- agent quality was shaken with potassium carbonate solution, separated and then distilled to remove most of the water. The sample so obtained was dried over anhydrous sodium sulphate and anhydrous potassium carbonate, decanted and then fractionally distilled. The densities of the purified liquids CH,Cl,, CH,ClCH,Cl, CHClCCl,, CCl,CCl,, c-C,H,, and methylethylke- tone measured at 303.15 + 0.01 K were found to be 1.30770, 1.23835, 1.45150, 1.60635, 0.76932, and 0.79450 g cme3 respectively which are in good agreement with the literature (Timmermans, 1950; Weissberger et al., 1955) values 1.30777, 1.23831, 1.4514, 1.60640, 0.76928, and 0.79452 g cm-3 respectively for the various liquids in the same order.

Excess volumes VE which are accurate to kO.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). Weights of the various liquids taken in the dilatometer were known with an accuracy to f0.0002 g. The experimental values of VE for the systems of methylethylketone with CH,Cl,, CH,ClCH,Cl, CHClCCl,, CCI,CCl, and C-C,H,, at various temperatures are given in Table 1, and have been fitted by the method of least squares to the equation

I/E=X,XZ[AO+A*(X1-X2)+A2(X1 -X2)2] (1)

where x1 refers to the mole fraction of methylethylketone, x2 refers to the mole fraction of the other component in the various systems, and A,, A, and A, are constants characteristic of a system at a given temperature. The values of the constants A,, A, and A, along with the standard deviations s(VE) for the various systems are given in Table 2. The values of VE for each system at one temperature have been plotted against mole fraction x1 of methylethylketone in Fig. 1 which shows that although VE curves are to

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TABLE 1

Experimental values of excess volumes VE for binary liquid mixtures a of methylethylketone with CH,Cl,, CH,ClCH,Cl, CHClCCl,, CCl,CCl, and C-C6H,, at various temperatures

Xl VE X1 VE (cm3 mol-‘) (cm3 mol-‘)

Methylethylketone + CH,CI, Temperature = 293.15 K 0.0343 0.019 0.0726 0.035 0.1492 0.055 0.1931 0.060 0.1971 0.061 0.2252 0.064 0.2519 0.060 0.3479 0.062 0.4306 0.060 0.5605 0.047 0.6338 0.039 0.6441 0.037 0.6991 0.032 0.7586 0.027 0.8203 0.020 0.8710 0.018 0.9216 0.014

Methylethylketone + CH,CICH,CI Temperature = 293.15 K 0.0711 - 0.005 0.1009 - 0.007 0.1781 - 0.010 0.2180 -0.013 0.2937 -0.015 0.3595 -0.017 0.4973 - 0.021 0.6080 - 0.030 0.6423 - 0.031 0.7135 - 0.034 0.7707 - 0.035 0.8473 - 0.030 0.9046 - 0.022

Methylethylketone + CHCICCI, Temperature = 298.15 K 0.0868 - 0.085 0.2080 - 0.159 0.2608 - 0.177 0.3212 - 0.190 0.3958 - 0.194 0.4511 - 0.205 0.5417 - 0.191 0.6714 - 0.163 0.7258 - 0.146 0.9085 - 0.062

Temperature = 303.15 K 0.0815 0.032 0.1572 0.043 0.1926 0.053 0.2576 0.054 0.3397 0.058 0.3837 0.057 0.4053 0.056 0.4595 0.055 0.5189 0.049 0.5912 0.045 0.7352 0.024 0.9296 0.007

Temperature = 303.15 K 0.0742 - 0.008 0.1665 - 0.022 0.2333 - 0.027 0.3468 - 0.038 0.4639 - 0.048 0.4817 - 0.047 0.6408 - 0.048 0.7014 - 0.044 0.7782 - 0.037 0.8811 - 0.021

Temperature = 308.15 K 0.1335 - 0.083 0.3080 - 0.184 0.4588 - 0.218 0.6078 -0.199 0.6465 -0.186 0.6662 -0.180 0.7171 - 0.163 0.8954 - 0.056 0.9407 - 0.029

(continued)

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TABLE 1 (continued)

Xl V’” Xl VE (cm3 mol-‘) (cm3 mol ’ )

Methylethylketone + CCI,CC12 Temperature = 293.15 K 0.1459 0.067 0.1886 0.078 0.3027 0.084 0.4343 0.068 0.4808 0.061 0.5493 0.050 0.6184 0.045 0.7003 0.042 0.7447 0.038

0.8207 0.029 0.8830 0.024 0.9260 0.013

Methylethylketone + c-C, H,, Temperature = 303.15 K 0.1967 0.717

0.2343 0.794 0.4412 0.947 0.5813 0.886 0.6338 0.841 0.7313 0.714 0.7482 0.678 0.8246 0.530 0.9575 0.159

Temperature = 303.15 K 0.2164 0.056 0.2802 0.061 0.4914 0.050 0.5416 0.037 0.5532 0.035 0.6336 0.033 0.6882 0.029 0.8891 0.013

a x1 refers to the mole fraction of methylethylketone.

TABLE 2

Values of the constants A,,, A, and A, in eqn. (1) and the standard deviation S( V’) for the various systems of methylethylketone

System Temperature A, A, A2 S( V”)

(K) (cm’ mol-‘) ( cm3 mol-‘) (cm’ mot-‘) (cm3 mot-‘)

methylethylketone 293.15 0.1964 - 0.1948 0.2087 0.0023 + CH,Cl, 303.15 0.1976 -0.1733 0.0813 0.0025

methylethylketone 293.15 + CH,CICH,Cl 303.15

methylethylketone 298.15 + CHClCCl 2 308.15

methylethylketone 293.15 + cc1 ,cc12 303.15

- 0.0964 - 0.1949

- 0.7840 - 0.8781

0.2439 0.1770

-0.1132 - 0.0487

-0.1107 0.0440

0.1951 -0.1838 0.0656 0.3763

- 0.2478 0.2601 - 0.1890 0.1685

0.0011 0.0015

0.0030 0.0030

0.0030 0.0034

methylethylketone + c-C,H,, 303.15 3.7396 - 0.7359 0.9937 0.0030

301

0.00

-0 .lO

-0.20

I I 1 I I

0.0 0.2 0.4 0.6 0.8

Xl

Fig. 1. Plot of VE against mole fraction of methylethylketone x1 for the various systems: 0, methylethylketone+ c-C,H,,, 303.15 K; A, methylethylketone+CCl,CCl,, 293.15 K; 0, methylethylketone+ CH,Cl,, 293.15 K; El, methylethylketone+ CH,ClCH,Cl, 303.15 K; V, methylethylketone + CHClCCl 2, 298.15 K.

some extent symmetrical with respect to composition in the case of the systems methylethylketone + C-C6H12, and methylethylketone + CHClCC12, these are highly asymmetrical in the case of the systems of methylethylke- tone with CH,Cl,, CCl,CCl, and CH,ClCH,Cl.

The data show that values of VE are slightly negative for methylethylke- tone + CH,ClCH,Cl and methylethylketone + CHClCCl,, slightly positive for methylethylketone + CH,Cl 2 and methylethylketone + CC1 &Cl 2, and highly positive for methylethylketone + c-C,H,,. The negative values of VE

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for the systems of methylethylketone with CHClCCl, and CH,ClCH,Cl indicate the existence of specific interaction of methylethylketone with CHClCCl, and CH,ClCH,Cl in the liquid state. The values of VE which are very slightly positive for methylethylketone + CH,Cl, and methylethyl- ketone + CCl,CCl,, as compared with VE for methylethylketone + C-C6Hi2, also indicate that there exists specific interaction of methylethylketone with CH,Cl, and CCl,CCl,. The data show that the values of the temperature coefficient (3VE/aT), are negative in the case of the systems of methyleth- ylketone with CH $1 2, CH ,ClCH ,Cl, CHClCCl 2 and CC1 &Cl 2, which can be visualized to be due to the predominance of the contribution to VE from dipolar forces over those from specific interactions. The specific interaction of methylethylketone with CH,ClCH,Cl, CHClCCl, and CH,Cl, can be visualized to be due to the formation of hydrogen bond on account of interaction of H atoms in the chloro-compounds with the lone-pair electrons on the oxygen atom of the ketone. There is, however, a possibility that CH,Cl,, CH,ClCH,Cl, CHClCCl 2 and CC1 &Cl 2 may be involved in the formation of charge-transfer complex with methylethylketone, owing to the interaction of Cl atoms in these chlorocompounds with the lone-pair elec- trons of methylethylketone.

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.

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Nath, J. and Dixit, A.P., 1984a. Ultrasonic velocities in, and adiabatic compressibilities and excess volumes for, binary liquid mixtures of acetone with tetrachloroethylene, trichloro- ethylene, methylene chloride, 1,2-dichloroethane, and cyclohexane. J. Chem. Eng. Data, 29: 313-316.

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