Density, refractive index, speed of sound, and viscosity have been measured of binary mixture dimethylsulfoxide (DMSO) + isopropylbenzene (CUMENE) over the whole composition range at 298.15, 303.15, 308.15, and 313.15 K and atmospheric pressure. From these experimental measurements the excess molar volume, deviations in viscosity, molar refractivity, speed of sound, and isentropic compressibility have been calculated. These deviations have been correlated by a polynomial Redlich-Kister equation to derive the coefficients and standard error. The viscosities have furthermore been correlated with two or three parameter models, that is, herric correlation and McAllister model, respectively.
This paper contributes in part to our ongoing research on the solution properties. In the present study, data on density, viscosity, refractive index and speed of sound of binary mixture dimethylsulfoxide (DMSO) + isopropylbenzene at 298.15, 303.15, 308.15, and 313.15 K have been measured experimentally. From these results the excess molar volumes, viscosity deviations, and deviations in molar refraction and isentropic compressibility have been derived. Dimethylsulfoxide is a versatile nonaqueous dipolar aprotic solvent having wide range of applications. It is used as a solvent in many nucleophilic substitutions reactions. It has the ability to pass through membranes, an ability that has been verified by numerous subsequent researchers. It can penetrate through living tissues without damaging them. Therefore local anesthetic or penicillin can be carried through the skin without using a needle which makes it a paramount in medicinal field.
Isopropylbenzene is a naturally occurring substance present in coal tar and petroleum, insoluble in water, but is soluble in many organic solvents. It is used as a feedback for the production of Phenol and its coproduct acetone. It is also used as a solvent for fats and raisins.
The study of the thermodynamic properties of DMSO + isopropylbenzene mixtures is of interest in industrial fields where solvent mixtures could be used as selective solvents for numerous reactions.
The chemicals used are of AR grade, dimethylsulfoxide (DMSO) and isopropylbenzene (CUMENE) are from Riedel, Germany. The chemicals are purified using standard procedure [
Physical properties of components at 298.15 K.
Component |
|
|
|
| |||
---|---|---|---|---|---|---|---|
exptl | lit | exptl | lit | exptl | lit | ||
DMSO | 298.15 | 1.0940 | 1.095379 | 1.9834 | 1.99109 | 1.4798 | 1.47759 |
CUMENE | 298.15 | 0.8581 | 0.857439 | 0.7388 | 0.73909 | 1.4928 | 1.48899 |
Density and Speed of sound were measured by ANTON PAAR densimeter (DSA 5000) to an accuracy of
Viscosities were measured by using calibrated modified Ubbelohde viscometer [
Flow time was measured with an electronic stop watch with precision of
Refractive indices were measured for sodium D-line by ABBE-3L refractometer having Bausch and Lomb lenses. The temperature was maintained constant with the water bath as described for the viscosity measurement. A minimum of three independent readings were taken for each composition, and the average value was considered in all the calculations. Refractive index data are accurate to ±0.0001 units.
At least three independent readings of all the physical property measurements on
Density,
|
|
|
| |
---|---|---|---|---|
|
g·cm−3 | mPa·s | m·s−1 | |
Dimethylsulfoxide(1) + isopropylbenzene(2) | ||||
298.15 K | ||||
| ||||
0.0000 | 0.8581 | 0.7388 | 1325 | 1.4928 |
0.1047 | 0.8721 | 0.8025 | 1336 | 1.4918 |
0.1866 | 0.8842 | 0.8603 | 1348 | 1.4909 |
0.3013 | 0.9031 | 0.9610 | 1365 | 1.4897 |
0.3835 | 0.9180 | 1.0397 | 1378 | 1.4887 |
0.5032 | 0.9421 | 1.1661 | 1400 | 1.4871 |
0.5858 | 0.9610 | 1.2692 | 1417 | 1.4859 |
0.6972 | 0.9895 | 1.4337 | 1442 | 1.4841 |
0.7926 | 1.0178 | 1.5896 | 1467 | 1.4829 |
0.8929 | 1.0519 | 1.7648 | 1493 | 1.4811 |
1.0000 | 1.0940 | 1.9834 | 1523 | 1.4798 |
| ||||
303.15 K | ||||
| ||||
0.0000 | 0.8538 | 0.6806 | 1313 | 1.4915 |
0.1047 | 0.8676 | 0.7519 | 1327 | 1.4905 |
0.1866 | 0.8797 | 0.8143 | 1339 | 1.4898 |
0.3013 | 0.8984 | 0.9064 | 1356 | 1.4885 |
0.3835 | 0.9132 | 0.9814 | 1369 | 1.4875 |
0.5032 | 0.9372 | 1.1086 | 1391 | 1.4859 |
0.5858 | 0.9559 | 1.2075 | 1408 | 1.4848 |
0.6972 | 0.9843 | 1.3691 | 1434 | 1.4829 |
0.7926 | 1.0122 | 1.5230 | 1459 | 1.4815 |
0.8929 | 1.0459 | 1.6943 | 1485 | 1.4796 |
1.0000 | 1.0890 | 1.8949 | 1512 | 1.4781 |
| ||||
308.15 K | ||||
| ||||
0.0000 | 0.8495 | 0.6167 | 1301 | 1.4896 |
0.1047 | 0.8632 | 0.6962 | 1317 | 1.4888 |
0.1866 | 0.8751 | 0.7616 | 1329 | 1.4881 |
0.3013 | 0.8936 | 0.8565 | 1346 | 1.4869 |
0.3835 | 0.9083 | 0.9294 | 1359 | 1.4859 |
0.5032 | 0.9322 | 1.0493 | 1381 | 1.4844 |
0.5858 | 0.9508 | 1.1459 | 1398 | 1.4833 |
0.6972 | 0.9788 | 1.3059 | 1425 | 1.4814 |
0.7926 | 1.0064 | 1.4565 | 1449 | 1.4799 |
0.8929 | 1.0404 | 1.6131 | 1473 | 1.4784 |
1.0000 | 1.0840 | 1.7979 | 1498 | 1.4765 |
| ||||
313.15 K | ||||
| ||||
0.0000 | 0.8452 | 0.5588 | 1289 | 1.4871 |
0.1047 | 0.8587 | 0.6434 | 1306 | 1.4864 |
0.1866 | 0.8705 | 0.7103 | 1319 | 1.4857 |
0.3013 | 0.8887 | 0.8063 | 1337 | 1.4846 |
0.3835 | 0.9033 | 0.8756 | 1349 | 1.4836 |
0.5032 | 0.9270 | 0.9947 | 1372 | 1.4821 |
0.5858 | 0.9454 | 1.0872 | 1389 | 1.4809 |
0.6972 | 0.9732 | 1.2459 | 1416 | 1.4792 |
0.7926 | 1.0008 | 1.3888 | 1439 | 1.4778 |
0.8929 | 1.0348 | 1.5402 | 1462 | 1.4762 |
1.0000 | 1.0786 | 1.7054 | 1486 | 1.4742 |
Density is used to evaluate excess molar volume calculated by the equation
Excess gibb’s free energy of activation has been also calculated using the viscosity and density of the mixture by the equation
The deviation in viscosity is obtained by equation
The experimental results for the speed of sound of binary mixture are listed in Table
Refractive indices have been used for the calculation of Molar refraction (
All the deviations (
Derived parameters of Redlich-Kister equation (
|
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|
---|---|---|---|---|---|
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|||||
| |||||
298.15 |
|
|
|
|
0.00561 |
303.15 |
|
|
0.5117 |
|
0.0055 |
308.15 |
|
|
0.7925 | 0.1613 | 0.0046 |
313.15 |
|
|
0.8186 | 0.1259 | 0.00549 |
| |||||
Δ | |||||
| |||||
298.15 |
|
|
0.0065 | 0.0645 | 0.00296 |
303.15 |
|
|
0.1384 | 0.0587 | 0.00178 |
308.15 |
|
|
0.2208 | 0.0967 | 0.00359 |
313.15 |
|
|
0.2922 | 0.141 | 0.00333 |
| |||||
|
|||||
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298.15 |
|
|
|
|
0.37123 |
303.15 |
|
|
|
|
0.21847 |
308.15 |
|
|
|
4.1751 | 0.27323 |
313.15 |
|
|
|
10.1465 | 0.51612 |
| |||||
Δ |
|||||
| |||||
298.15 |
|
0.2009 | −0.1111 |
|
0.0089 |
303.15 |
|
0.1994 | 0.0606 |
|
0.0056 |
308.15 |
|
0.2093 | 0.2408 |
|
0.0127 |
313.15 |
|
0.1947 | 0.3148 |
|
0.0167 |
| |||||
|
|||||
| |||||
298.15 | 133.9592 | 209.2619 | 16.9998 | 168.234 | 64.9657 |
303.15 | 246.905 | 198.0077 | 349.8235 | 15.7865 | 3.63471 |
308.15 | 488.086 | 69.5143 | 603.5378 | 59.8815 | 7.55398 |
313.15 | 724.2593 |
|
832.3713 | 64.9657 | 8.13559 |
The deviations in excess molar volume at 298.15 to 313.15 K versus the mole fraction of DMSO are shown in Figure
Experimental and calculated excess molar for the DMSO(1) + CUMENE(2) at ♦, 298.15 K; ■, 303.15 K; ▲, 308.15 K; ×, 313.15 K; symbols represent the experimental values; lines are optimised by Redlich-Kister parameters.
The viscosity and deviations are presented in Table
Experimental and calculated deviations in viscosity for DMSO(1) + CUMENE(2) at ♦, 298.15 K; ■, 303.15 K; ▲, 308.15 K; ×, 313.15 K; symbols represent the experimental values; lines are optimised by Redlich-Kister parameters.
The viscosity data is also fitted to the two- and the three-parameter model, that is, herric correlation and the McAllister model and the evaluated parameters are presented in Table
Interaction parameters for the McAllister model (
|
|
|
|
---|---|---|---|
McAllister model | |||
| |||
298.15 | 0.975300 | 0.909494 | 0.00014 |
303.15 | 0.968905 | 0.905236 | 0.00032 |
308.15 | 0.962426 | 0.900935 | 0.00044 |
313.15 | 0.958670 | 0.900372 | 0.00051 |
| |||
|
|
|
|
| |||
Herric correlation | |||
| |||
298.15 |
|
|
0.00014 |
303.15 |
|
|
0.00032 |
308.15 |
|
|
0.00044 |
313.15 |
|
|
0.00052 |
The deviations in molar refraction are shown in Figure
Experimental and calculated deviations in molar refraction for DMSO(1) + CUMENE(2) at ♦, 298.15 K; ■, 303.15 K; ▲, 308.15 K; ×, 313.15 K; symbols represent the experimental values; lines are optimised by Redlich-Kister parameters.
The results of derived
Experimental and calculated deviations in isentropic compressibility for DMSO(1) + CUMENE(2) at ♦, 298.15 K; ■, 303.15 K; ▲, 308.15 K; ×, 313.15 K; symbols represent the experimental values; lines are optimised by Redlich-Kister parameters.
Experimental and calculated deviations in Gibbs free energy of activation for DMSO(1) + CUMENE(2) at ♦, 298.15 K; ■, 303.15 K; ▲, 308.15 K; ×, 313.15 K; symbols represent the experimental values; Lines are optimised by Redlich-Kister parameters.
Parameters of Redlich-Kister equation
Interaction coefficient of McAllister model
Coefficients of Herric’s correlation
Kinematic viscosity (
Density (g/cm³)
Standard deviation
Expansion coefficient
Viscosity (cP)
Excess Gibbs free energy (J/mol)
Excess molar volume
Excess isentropic compressibility
Universal gas constant (8.314 J/mol.K)
Absolute temperature (K)
Volume fraction (dimensionless).