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 (1989) 297-303 Elsevier Science Publishers B.V.. Amsterdam

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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

Chemistry Department, (Received

SAINI

Gorakhpur

March 2, 1989; accepted

University, Gorakhpur-273009

(India)

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 (CHClCC1 2), tetrachloroethylene (CC1 &Cl 2) and cyclohexane (c-C,H,,) at various temperatures, and it has been pointed out that there exist specific interactions between acetone and these chloro-compounds. However, extensive studies concerning interactions of chloroalkanes and chloroalkenes with ketones of varying molecular complexity have not been carried out previously, and the binary systems of methylethylketone with CH,Cl 2, CH,ClCH,Cl, CHClCCl,, CCl,CCl, are of considerable interest from the above 037%3812/89/$03.50

Q 1989 Elsevier Science Publishers

B.V.

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viewpoint. The system methylethylketone + C-CgH12, in which case nonspecific 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, CHClCcl,, CCl,CCl, and C-CgH12, and the results obtained are discussed here. Cyclohexane (BDH) of reagent grade was purified by the method described by Adcock and McGlashan (1954), and 1,2-dichloroethane (BDH) was purified as described by Foster and Fyfe (1966). Spectral grade tetrachloroethylene (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 reagent 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 methylethylketone 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

299 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 (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

X1

VE (cm3 mol-‘)

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)

300 TABLE

1 (continued) V’” (cm3 mol-‘)

Xl

VE (cm3 mol

Xl

Methylethylketone + CCI,CC12 Temperature = 293.15 K 0.1459 0.067 0.078 0.1886 0.3027 0.084 0.4343 0.068 0.4808 0.061 0.050 0.5493 0.6184 0.045 0.042 0.7003 0.7447 0.038 0.8207 0.029 0.024 0.8830 0.9260 0.013

Temperature 0.2164 0.2802 0.4914 0.5416 0.5532 0.6336 0.6882 0.8891

’)

= 303.15 K 0.056 0.061 0.050 0.037 0.035 0.033 0.029 0.013

Methylethylketone + c-C, H,, Temperature = 303.15 K 0.717 0.1967 0.794 0.2343 0.947 0.4412 0.886 0.5813 0.6338 0.841 0.7313 0.714 0.7482 0.678 0.8246 0.530 0.9575 0.159 a x1 refers to the mole fraction TABLE

of methylethylketone.

2

Values of the constants A,,, A, and A, in eqn. (1) and the standard various systems of methylethylketone System

Temperature (K)

A, (cm’ mol-‘)

A, ( cm3 mol-‘)

deviation

S( V’)

for the

A2

S( V”)

(cm’ mot-‘)

(cm3 mot-‘)

methylethylketone + CH,Cl,

293.15 303.15

0.1964 0.1976

- 0.1948 -0.1733

0.2087 0.0813

0.0023 0.0025

methylethylketone + CH,CICH,Cl

293.15 303.15

- 0.0964 - 0.1949

-0.1132 - 0.0487

-0.1107 0.0440

0.0011 0.0015

methylethylketone + CHClCCl 2

298.15 308.15

- 0.7840 - 0.8781

0.1951 0.0656

-0.1838 0.3763

0.0030 0.0030

methylethylketone + cc1 ,cc12

293.15 303.15

0.2439 0.1770

- 0.2478 - 0.1890

0.2601 0.1685

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 0.0

I

0.2

1

I

I

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 + CHClCC12, systems methylethylketone + C-C6H12, and methylethylketone these are highly asymmetrical in the case of the systems of methylethylketone with CH,Cl,, CCl,CCl, and CH,ClCH,Cl. The data show that values of VE are slightly negative for methylethylketone + 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

302

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 methylethylketone + 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 methylethylketone 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 electrons 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. REFERENCES Adcock, D.S. and McGlashan, M.L., 1954. Heats of mixing. Proc. R. Sot., London, Ser. A, 226: 266-282. Foster, R. and Fyfe, C.A., 1966. Electron-donor-acceptor complex formation by compounds of biological interest. Part III. Indole complexes. J. Chem. Sot. B: 926-929. Nath, J. and Dixit, A.P., 1984a. Ultrasonic velocities in, and adiabatic compressibilities and excess volumes for, binary liquid mixtures of acetone with tetrachloroethylene, trichloroethylene, methylene chloride, 1,2-dichloroethane, and cyclohexane. J. Chem. Eng. Data, 29: 313-316. Nath, J. and Dixit, A.P., 198413. Binary systems of acetone with tetrachloroethylene, trichloroethylene, methylene chloride, 1,2-dichloroethane, and cyclohexane. 2. Viscosities at 303.15 K. J. Chem. Eng. Data, 29: 317-319. Nath, J. and Dixit, A.P., 1985. Binary systems of acetone with tetrachloroethylene, trichloroethylene, methylene chloride, 1,2-dichloroethane and cyclohexane. Part 3-Dielectric properties and refractive indices at 303.15 K. J. Chem. Sot. Faraday Trans. 2, 81: 11-19.

303 Nath, J. and Dubey, S.N., 1979. Excess volumes for trichloroethylene + benzene, + toluene, + p-xylene, + tetrachloromethane, and + trichloromethane at 303.15 K. J. Chem. Thermodyn., 11: 1163-1165. Nath, J. and Singh, 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 Singh, 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. Timmermans, J., 1950. Physico-Chemical Constants of Pure Organic Compounds. Elsevier, Amsterdam. Weissberger, A., Proskauer, E.S., Riddick, J.A. and Toops, E.E., Jr., 1955. Technique of Organic Chemistry, Vol. VII, Wiley Interscience, New York.