Densities, viscosities, and speed of sound have been determined at
The excess or deviation properties of liquid-liquid mixtures are useful in several industrial applications owing to their influence upon the effectiveness of the operations. Nowadays, the determination of ultrasonic velocity and the related acoustical parameters derived from it has attracted the attention of several researchers. Much work has been done in solutions of polymers [
Tetrahydrofuran is a polar
In view of the abovementioned significances, these solvents are chosen with an aim to investigate the effect of the presence of two lone pairs of electrons on the oxygen atom of ether, when it is mixed with methyl benzoate. Moreover, it would be interesting to know the behavior of ether in an environment of aromatic ester molecules. The main objective of the present study is to determine the density
In our earlier papers [
Methyl benzoate (Fluka AG >0.996), tetrahydrofuran, 1,4-dioxane, anisole, and butyl vinyl ether (all Sigma-Aldrich, AR grade) of mass purity >0.997 were used without further purification. These chemicals were kept over molecular sieves for several days before use. The mass fraction purities as determined by gas chromatography (HP 8610) using FID were as follows: methyl benzoate (>0.996), tetrahydrofuran, (>0.996), 1,4-dioxane, (>0.998), anisole, (>0.998), and butyl vinyl ether (>0.997). The purity of the samples was further checked by comparing the measured density
Comparison of experimental density
Liquid |
|
|
|
||
---|---|---|---|---|---|
Exptl. | Lit. | Exptl. | Lit. | ||
Methyl benzoate | 303.15 | 1.0785 | 1.0788 [ |
1.678 | 1.673 [ |
1.0790 [ |
1.656 [ | ||||
308.15 | 1.0743 | 1.0740 [ |
1.517 | 1.510 [ | |
1.0741 [ |
|||||
1.504 [ | |||||
1.07399 [ |
1.510 [ | ||||
313.15 | 1.0696 | 1.0690 [ |
1.373 | 1.365 [ | |
| |||||
Tetrahydrofuran | 303.15 | 0.8787 | 0.8771 [ |
0.439 | |
308.15 | 0.8730 | 0.87214 [ |
0.429 | ||
313.15 | 0.8669 | 0.86719 [ |
0.390 | ||
| |||||
1,4-Dioxane | 303.15 | 1.0227 | 1.02271 [ |
1.090 | 1.102 [ |
1.095 [ | |||||
308.15 | 1.0178 | 1.0172 [ |
0.999 | 1.008 [ | |
313.15 | 1.0116 | 1.01132 [ |
0.946 | 0.946 [ | |
| |||||
Anisole | 303.15 | 0.9853 | 0.984374 [ |
0.923 | 0.931 [ |
308.15 | 0.9792 | 0.9788 [ |
0.849 | 0.849 [ | |
313.15 | 0.9728 | 0.764 | |||
| |||||
Butyl vinyl ether | 303.15 | 0.7741 | 0.387 | ||
308.15 | 0.7682 | 0.365 | |||
313.15 | 0.7633 | 0.354 |
Binary mixtures were prepared by mass in airtight ground stoppered bottles. Mass measurements accurate to ±0.01 mg were made on a digital electronic balance (Mettler AE 240, Switzerland). The resulting uncertainty in mole fraction was estimated to be less than ±0.0001. Each mixture was immediately used after it was well mixed by shaking. The densities of the pure and their binary mixtures were determined by using an Anton Paar density meter (DMA 4100). The uncertainty in the density measurements was found to be less than ±0.0004 g·cm−3.
Viscosities were determined using an Ubbelohde viscometer with an uncertainty of ±0.008 mPa.s. The detailed method of measurement of viscosity has been reported earlier [
The experimental values of densities
Values of density
|
|
|
|
|
|
---|---|---|---|---|---|
Methyl benzoate (1) + tetrahydrofuran (2) | |||||
| |||||
| |||||
0.0689 | 0.9020 |
|
0.496 | 1260 | 698 |
0.1417 | 0.9246 |
|
0.562 | 1272 | 669 |
0.2202 | 0.9468 |
|
0.638 | 1284 | 641 |
0.3030 | 0.9680 |
|
0.727 | 1296 | 615 |
0.3932 | 0.9885 |
|
0.829 | 1308 | 591 |
0.4930 | 1.0084 |
|
0.951 | 1320 | 569 |
0.6018 | 1.0272 |
|
1.096 | 1332 | 549 |
0.7225 | 1.0452 |
|
1.262 | 1344 | 530 |
0.8535 | 1.0623 |
|
1.446 | 1356 | 512 |
| |||||
| |||||
0.0689 | 0.8964 |
|
0.484 | 1232 | 735 |
0.1417 | 0.9192 |
|
0.546 | 1236 | 712 |
0.2202 | 0.9413 |
|
0.616 | 1244 | 686 |
0.3030 | 0.9627 |
|
0.699 | 1256 | 659 |
0.3932 | 0.9833 |
|
0.790 | 1268 | 633 |
0.4930 | 1.0033 |
|
0.904 | 1284 | 605 |
0.6018 | 1.0222 |
|
1.032 | 1300 | 679 |
0.7225 | 1.0403 |
|
1.181 | 1316 | 555 |
0.8535 | 1.0575 |
|
1.343 | 1336 | 530 |
| |||||
| |||||
0.0689 | 0.8905 |
|
0.443 | 1216 | 759 |
0.1417 | 0.9134 |
|
0.505 | 1220 | 736 |
0.2202 | 0.9358 |
|
0.567 | 1228 | 709 |
0.3030 | 0.9572 |
|
0.641 | 1240 | 679 |
0.3932 | 0.9779 |
|
0.729 | 1252 | 652 |
0.4930 | 0.9980 |
|
0.830 | 1268 | 623 |
0.6018 | 1.0171 |
|
0.943 | 1284 | 596 |
0.7225 | 1.0354 |
|
1.078 | 1300 | 572 |
0.8535 | 1.0527 |
|
1.220 | 1320 | 545 |
| |||||
Methyl benzoate (1) + 1,4-dioxane (2) | |||||
| |||||
| |||||
0.0898 | 1.0307 |
|
1.130 | 1328 | 550 |
0.1468 | 1.0355 |
|
1.157 | 1336 | 541 |
0.2280 | 1.0421 |
|
1.198 | 1344 | 531 |
0.3145 | 1.0485 |
|
1.244 | 1352 | 521 |
0.4054 | 1.0543 |
|
1.293 | 1360 | 513 |
0.5056 | 1.0599 |
|
1.352 | 1368 | 504 |
0.6161 | 1.0653 |
|
1.418 | 1372 | 499 |
0.7316 | 1.0701 |
|
1.491 | 1372 | 496 |
0.8597 | 1.0749 |
|
1.573 | 1372 | 494 |
| |||||
| |||||
0.0898 | 1.0261 |
|
1.038 | 1324 | 556 |
0.1468 | 1.0311 |
|
1.066 | 1332 | 547 |
0.2280 | 1.0377 |
|
1.106 | 1340 | 537 |
0.3145 | 1.0440 |
|
1.147 | 1348 | 530 |
0.4054 | 1.0499 |
|
1.192 | 1352 | 521 |
0.5056 | 1.0555 |
|
1.246 | 1356 | 515 |
0.6161 | 1.0608 |
|
1.308 | 1360 | 510 |
0.7316 | 1.0655 |
|
1.376 | 1360 | 507 |
0.8597 | 1.0702 |
|
1.449 | 1360 | 505 |
| |||||
| |||||
0.0898 | 1.0205 |
|
0.984 | 1320 | 562 |
0.1468 | 1.0257 |
|
1.006 | 1328 | 553 |
0.2280 | 1.0326 |
|
1.040 | 1336 | 543 |
0.3145 | 1.0390 |
|
1.075 | 1340 | 536 |
0.4054 | 1.0450 |
|
1.110 | 1348 | 527 |
0.5056 | 1.0507 |
|
1.157 | 1352 | 521 |
0.6161 | 1.0560 |
|
1.208 | 1356 | 515 |
0.7316 | 1.0608 |
|
1.263 | 1356 | 513 |
0.8597 | 1.0655 |
|
1.324 | 1356 | 510 |
| |||||
Methyl benzoate (1) + Anisole (2) | |||||
| |||||
| |||||
0.0860 | 0.9950 |
|
0.974 | 1388 | 522 |
0.1821 | 1.0056 |
|
1.038 | 1380 | 522 |
0.2756 | 1.0157 |
|
1.101 | 1372 | 523 |
0.3978 | 1.0282 |
|
1.187 | 1368 | 520 |
0.4637 | 1.0347 |
|
1.234 | 1368 | 516 |
0.5659 | 1.0442 |
|
1.307 | 1368 | 512 |
0.6701 | 1.0534 |
|
1.391 | 1368 | 507 |
0.7776 | 1.0624 |
|
1.480 | 1368 | 503 |
0.8850 | 1.0710 |
|
1.572 | 1368 | 499 |
| |||||
| |||||
0.0860 | 0.9891 |
|
0.894 | 1368 | 540 |
0.1821 | 1.0000 |
|
0.949 | 1356 | 544 |
0.2756 | 1.0102 |
|
1.007 | 1352 | 542 |
0.3978 | 1.0229 |
|
1.086 | 1348 | 538 |
0.4637 | 1.0295 |
|
1.129 | 1348 | 535 |
0.5659 | 1.0392 |
|
1.195 | 1348 | 530 |
0.6701 | 1.0485 |
|
1.272 | 1348 | 525 |
0.7776 | 1.0576 |
|
1.355 | 1348 | 520 |
0.8850 | 1.0663 |
|
1.439 | 1348 | 516 |
| |||||
| |||||
0.0860 | 0.9830 |
|
0.800 | 1356 | 553 |
0.1821 | 0.9941 |
|
0.850 | 1344 | 557 |
0.2756 | 1.0045 |
|
0.902 | 1340 | 554 |
0.3978 | 1.0174 |
|
0.972 | 1336 | 551 |
0.4637 | 1.0241 |
|
1.012 | 1336 | 547 |
0.5659 | 1.0340 |
|
1.074 | 1336 | 541 |
0.6701 | 1.0435 |
|
1.144 | 1336 | 537 |
0.7776 | 1.0528 |
|
1.220 | 1336 | 532 |
0.8850 | 1.0616 |
|
1.301 | 1336 | 528 |
| |||||
Methyl benzoate (1) + Butyl vinyl ether (2) | |||||
| |||||
| |||||
0.1026 | 0.8056 |
|
0.437 | 1104 | 1019 |
0.2055 | 0.8375 |
|
0.497 | 1128 | 938 |
0.3060 | 0.8690 |
|
0.571 | 1152 | 867 |
0.4047 | 0.8999 |
|
0.657 | 1176 | 804 |
0.5057 | 0.9313 |
|
0.761 | 1204 | 741 |
0.6065 | 0.9623 |
|
0.891 | 1232 | 685 |
0.7061 | 0.9926 |
|
1.038 | 1260 | 635 |
0.8034 | 1.0218 |
|
1.205 | 1292 | 586 |
0.9021 | 1.0511 |
|
1.422 | 1328 | 540 |
| |||||
| |||||
0.1026 | 0.8001 |
|
0.421 | 1092 | 1048 |
0.2055 | 0.8322 |
|
0.478 | 1116 | 965 |
0.3060 | 0.8637 |
|
0.546 | 1136 | 891 |
0.4047 | 0.8947 |
|
0.657 | 1160 | 825 |
0.5057 | 0.9261 |
|
0.626 | 1188 | 760 |
0.6065 | 0.9572 |
|
0.720 | 1216 | 702 |
0.7061 | 0.9875 |
|
0.974 | 1248 | 650 |
0.8034 | 1.0168 |
|
1.124 | 1280 | 600 |
0.9021 | 1.0462 |
|
1.319 | 1316 | 552 |
| |||||
| |||||
0.1026 | 0.7954 |
|
0.400 | 1084 | 1070 |
0.2055 | 0.8275 |
|
0.452 | 1108 | 984 |
0.3060 | 0.8591 |
|
0.515 | 1132 | 908 |
0.4047 | 0.8901 |
|
0.585 | 1156 | 841 |
0.5057 | 0.9215 |
|
0.671 | 1184 | 774 |
0.6065 | 0.9526 |
|
0.778 | 1212 | 715 |
0.7061 | 0.9829 |
|
0.897 | 1244 | 657 |
0.8034 | 1.0121 |
|
1.034 | 1276 | 607 |
0.9021 | 1.0414 |
|
1.205 | 1308 | 561 |
The excess volume
The isentropic compressibilities
Derived parameters of excess functions by Redlich-Kister equation and standard deviations
Function |
|
|
|
|
|
|
---|---|---|---|---|---|---|
Methyl benzoate (1) + tetrahydrofuran (2) | ||||||
|
303.15 |
|
1.2905 | 1.1561 | — | 0.003 |
308.15 |
|
1.2879 | 1.1173 | — | 0.003 | |
313.15 |
|
1.2921 | 1.9336 | — | 0.004 | |
|
303.15 |
|
0.0783 |
|
— | 0.002 |
308.15 |
|
0.0762 |
|
— | 0.002 | |
313.15 |
|
0.0052 |
|
— | 0.001 | |
|
303.15 | 1303.56 | 9.2800 |
|
|
2.5 |
308.15 | 1332.27 |
|
|
|
3.3 | |
313.15 | 1442.68 |
|
50.2305 |
|
3.8 | |
|
303.15 |
|
7.2762 |
|
1.4106 | 0.008 |
308.15 |
|
|
3.5145 |
|
0.093 | |
313.15 |
|
0.5719 | 4.7747 | 1.1539 | 0.090 | |
| ||||||
Methyl benzoate (1) + 1,4-dioxane (2) | ||||||
|
303.15 |
|
0.290 | 0.846 | — | 0.002 |
308.15 |
|
0.425 | 0.753 | — | 0.002 | |
313.15 |
|
0.552 | 0.575 | — | 0.003 | |
|
303.15 |
|
0.018 |
|
— | 0.001 |
308.15 |
|
0.007 | 0.009 | — | 0.001 | |
313.15 |
|
0.019 | 0.045 | — | 0.001 | |
|
303.15 | 152.594 | 48.243 |
|
|
0.7 |
308.15 | 191.571 | 23.232 | 37.394 |
|
2.8 | |
313.15 | 201.888 | 29.749 | 100.81 |
|
2.4 | |
|
303.15 |
|
1.8216 | 3.7965 |
|
0.094 |
308.15 |
|
2.7930 |
|
|
0.044 | |
313.15 |
|
2.1793 |
|
|
0.048 | |
| ||||||
Methyl benzoate (1) + anisole (2) | ||||||
|
303.15 |
|
0.2637 | 0.5566 | — | 0.003 |
308.15 |
|
|
0.4368 | — | 0.003 | |
313.15 |
|
|
0.2005 | — | 0.002 | |
|
303.15 |
|
0.0055 | 0.0234 | — | 0.002 |
308.15 |
|
|
|
— | 0.001 | |
313.15 |
|
|
|
— | 0.002 | |
|
303.15 | 177.724 |
|
99.649 | 70.211 | 2.2 |
308.15 | 116.959 |
|
12.737 | 80.252 | 2.5 | |
313.15 | 56.636 |
|
|
63.520 | 1.2 | |
|
303.15 | 3.5076 |
|
0.9701 | 5.8130 | 0.036 |
308.15 | 4.7056 |
|
5.0184 | 4.5773 | 0.053 | |
313.15 | 5.3764 |
|
6.5667 | 2.5075 | 0.050 | |
| ||||||
Methyl benzoate (1) + butyl vinyl ether (2) | ||||||
|
303.15 |
|
|
1.0922 | — | 0.004 |
308.15 |
|
|
0.9973 | — | 0.004 | |
313.15 |
|
|
0.9846 | — | 0.005 | |
|
303.15 |
|
|
|
— | 0.002 |
308.15 |
|
|
|
— | 0.003 | |
313.15 |
|
|
|
— | 0.003 | |
|
303.15 |
|
174.93 |
|
|
5.8 |
308.15 |
|
153.92 |
|
|
7.2 | |
313.15 |
|
106.49 | 131.85 |
|
5.7 | |
|
303.15 |
|
5.1677 | 5.1277 |
|
0.080 |
308.15 |
|
5.1564 | 3.8155 |
|
0.085 | |
313.15 |
|
3.8500 |
|
2.8527 | 0.072 |
The variations of excess volume tetrahydrofuran > butyl vinyl ether > 1,4-dioxane > anisole
The effect of temperature on
Curves of excess volumes (
The results of butyl vinyl ether > tetrahydrofuran > anisole > 1,4-dioxane
It is observed that negative values of
Curves of deviation in viscosity (
The dependence of
Curves of excess Gibb’s free energy of activation of viscous flow (
The plots of
Curves of deviation in isentropic compressibility (
The densities
The financial support from University Grants Commission, New Delhi, India, through Major Research Project (no. 38-24/2009 SR) to the corresponding author (M. V. Rathnam) is gratefully acknowledged. The authors also sincerely express their gratitude to the editor-in-chief and the reviewers for their valuable comments.