Densities, viscosities and excess thermodynamic properties of ternary liquid mixtures of nitrobenzene with polar and non-polar solvents at 298.15 K

Densiti es, viscosities and excess th ermodynamic prope rti es of te rnary liquid

mixtures of nitrobe nze ne with polar and non-polar so lve nts at 298.15 K

Poonum Ruthorc & _ Mukhtar Sinohb ^a. '"

Department of Chemistry. Agra College. Agra 2~2 002. India Email: lllukhtarsingh20ln@redilTmail.com

Receilwl 12 Septelllber 2005; rerel'ised 12 Gerober 2006

Densities and viscosities of ternary liquid mixtures of nitrobenzene + methyl alcohol + (benzene: + tolucne: + carbon tetrachloride: + I A-dioxane) have been determined at 298.15 K.

From density and viscosity d:lta. values of viscosity deviations and thermodynamic excess properties. viz .. excess molar volume and excess Gibbs free energy of activation of viscous now for the ternary mixtures have been determined and fitted to Cibulka's equation. The results of the study show that experimental values of these properties arc in close agreement with those predicted by Cibulka's equation.

I PC Code: GO I 9/00; GO I N I 1/00

In continuation of earlier studiesl.2

on the determi- nation of densities, viscosities and excess thermo- dynamic properties of ternary liquid mixtures of ethane 1,2 diol and pyridine with polar and non-polar solvent, we report herein studies on the determination of densities, viscosities viscosity deviations (L''.11) and excess thermodynamic properties (V^t:· and

!Jet

^{l/:) of the}

ternary liquid mixtures of nitrobenzene with polar and non-polar solvents at 298.ISK. The experimental values of [0,11,

v"

and [o,C^IlE have been correlated with those predicted by Cibulka's equation for the following ternary liquid mixtures: (i) nitrobenzene

+

methyl alcohol

+

benzene; (ii) nitrobenzene

+

methyl alcohot

+

toluene; (iii) nitrobenzene

+

methyl alcohol + carbon tetrachloride, and (iv) nitrobenzene + methyl alcohol

+

I

A

dioxane.

Experimental

All the organic liquids used in the present study were of analytical grade and were obtained from Merck. They were further puri fied accordi ng to the procedu re descri bed in Ii teratu re^J·s.

"Present address: H.I.G.142. Phase A. Shastri Puram, P.O. Sikandara. Agra 282 007. India

Liquid mixtures of various compositions were prepared by mass in a 25 ml flask using a Mettler analytical balance. The uncertainty in the mole fraction of the mixtures was estimated ro be less than

±O.OOO I. Density and viscosity measurements were carried out using a thermostatically controlled, well- stirred water bath, where temperatures were measured with a digital thermometer with an accuracy of

±0.01 K.

Densities of pure liquids and ternary liquid mixtures were measured at 298.15 K with an Anton Parr digital vibrating tube densimeter. The uncertainty of the density measurements was estimated to be less than ± I x 1 O-~ g.cm-'. The viscosities (11) of pure organic liquids and their ternary liquid mixtures were determi ned usi ng an Ostwald viscometer wh ich was suspended In a thermostat maintained at

298. 1 S±O.O

I K. The details of the procedure have been reported earlie/'. The uncertainty of calculated absolute viscosities was ± IxI0·⁴mPa.s.

Results and discussion

Densities (p) and viscosities (11) of ternary liquid mixtures involving nitrobenzene as the first compo- nent, methyl alcohol as the second component and benzene/toluene/carbon tetrachloride/ I A-dioxane as the third non-polar component were measured at 29S.IS ± 0.0 I K as a function of composition of the ternary liquid mixtures. The results of studies arc presented in Table I. On plotting experimental values of p and 11 against the mole fraction of first compo- nent (XI)' it is seen that the variation of p and 11 over the entire range of composition is non-linear (vide representative Fig. I) indicating the presence of molecular interactions bet ween the mix i ng compo- nents of the ternary mixtures⁷.s.

The viscosity deviations, excess molar volumes and excess molar Gibbs free energies of activation of viscous flow for ternary mixtures were determined using the following equations'J·to.

/I

[0,11=11- L.xilli . .. (I)

i;tl

where Xi, l1i and 11 refer respectively to the mole fraction and viscosities of the ith pure component and of the mixtures.

NOTES 2651

Tnble I-Dcnsities, viscosities, viscosity devintions nnd thermodynnillic excess properties of ternnry liquid mixtures nt 298.15 K

0.0789 0.1132 0.1437 0.1721 0.1982 0.2218 0.2440 0.2645 0.2949 0.3399 0.4071 0.4654 0.5304 0.6389 0.6855 0.7795 0.8310 0.8310

0.0892 0.1251 0.1558 0.1835 0.2081 0.2297 0.2495 0.2674 0.2963 0.3416 0.4123 0.4716 0.5379 0.6538 0.6965 0.7929 0.8373 0.8373

0.0834 0.1184 0.1491 0.1772 0.2028

0.2002 0.2860 0.3644 0.4356 0.5010 0.5616 0.6173 0.6685 0.6717 0.6252 0.5154 0.4529 0.3832 0.2156 0.2167 0.1159 0.1168 0.1168

0.2261 0.3162 0.3952 0.4645 0.5260 0.5818 0.6312 0.6758 0.6750 0.6284 0.5219 0.4590 0.3886 0.2206 0.2202 0.1179 0.1177 0.1177

0.2115 0.2993 0.3782 0.4486 0.5125

.r1

0.7209 0.6008 0.4919 0.3924 0.3007 0.2166 0.1386 0.0670 0.0334 0.0349 0.0775 0.0817 0.0864 0.1455 0.0978 0.1046 0.0522 0.0522

0.6847 0.5587 0.4490 0.3520 0.2659 0.1885 0.1193 0.0568 0.0287 0.0300 0.0658 0.0694 0.0735 0.1256 0.0833 0.0892 0.0450 0.0450

0.7051 0.5823 0.4727 0.3742 0.2847

P -J

g ^elll

1.0082 1.0402 1.1093 1.1408 1.1731 1.1780 1.2201 1.2485 1.2790 1.2761 1.2840 1.2955 1.3220 1.3168 1.3477 1.3022 1.2892 1.2892

0.8962 0.9073 0.9287 0.9511 0.9659 0.9798 0.9959 1.0095 1.0276 1.0718 I.()919 1.1090 1.1237 1.1350 1.1546 1.1631 1.1798 1798

1.8640 1.8980 1.8829 1.7540 1.6209

11 IllPa.s

fill IllPn.s

fill

*

V VI:

vI: *

fiC#!: fiCn ", J 11101-¹ I1lPa.s cm'1ll01-¹ cnr¹mol ¹ cm'lllol-¹ J mol-^I

Nilmbellzelle + Melhyl ([Icohol + Bell;,clle

0.7719 0.8236 0.8771 0.8844 0.9410 0.9511 0.9636 0.9950 1.0203 1.0889 1.1785 1.2322 1.3144 1.3943 1.4491 1.5516 1.5865 1.5865

0.4953 0.4439 0.4152 0.4085 0.4241 0.4638 0.5312 0.6360 0.7891 0.9192 0.9794 0.9328 0.9902 1.0537 1.0521 1.2079 1.3103 1.4760

0.1271 0.1436 0.1659 0.1441 0.1740 0.1599 0.1498 0.160 I 0.1531 0.1731 0.1894 0.1801 0.1920 0.1538 0.1590 0.1599 0.1400 0.1400

0.1474 0.1797 0.1678 0.1470 0.1325 0.1304 0.1419 0.1645 0.1954 0.2134 0.2334 0.1899 0.1812 0.1725 0.1543 0.1762 0.1447 0.1655

71.851 67.321 61.112 57.676 54.504 52.817 49.705 47.429 47.251 50.624 56.608 60.355 63.786 73.609 73.438 82.821 85.422 85.422

NilmbclI;,clle + Mel/n'l ([/coho/ + Toilielle

0.9672 1.0092 1.2100 1.2500 1.3420 1.3520 1.3346 1.2955 1.4975 1.6362 1.5200 1.7700 1.8500 2.1990 2.1000 1.8410 1.2500 1.2500

0.6372 0.9583 1.4424 1.9597 2.3494 2.4644 2.2771 1.8939 1.4377 1.2812 1.4187 2.1063 2.3445 2.5412 2.9771 2.5271 2.1491 1.9180

0.3400 03400 0.5049 0.5125 0.5758 0.5605 0.5200 0.4600 0.6300 0.7199 0.5282 0.7142 0.7227 0.9479 0.8017 0.4387 0.2013 0.2013

0.3465 0.3590 0.5065 0.5361 0.640 I 0.6148 0.5359 0.4362 0.6435 0.7365 0.5471 06860 0.7260 0.9512 0.8132 0.3966 0.2152 0.2341

90.728 84.875 78.835 73.498 69.334 65.614 62.189 59.242 59.115 60.599 67.353 71.381 76.038 87.340 87.024 94.242 94.085 94.085

-9.500 -8.462 395.107 378.855 -10.200 -9.580 470.210 464.953 -12.900 -11.184 456.826 48l.513 -13.166 -12.080 394.086 341.512 -13.400 -12.632 467.699 438.564 -12.384 -12.921 469.659 442.482 -13.000 -12.937 400.159 420.227 -13.000 -12.623 406.871 395.745 -13.400 -11.927 376.153 386.767 -12.900 -11.795 482.169 487.779 -13.210 -12.526 532.633 557.525 -13.297 -14.276 501.463 529.509 -14.142 -14.870463.519496.097 -14.000 -15.236 298.609 309.306 -14.700 -15.770 252.407 280.188 -I 1.500 -14.278 235.790 250.604 -9.500 -9.745 217.101 225.800 -9.500 -9.172 217.101 227.194

-1.150 -0.830 -1.461 -2.050 -2.000 -1.900 -1.940 -1.830 -1.880 -3.300 -3.330 -3.230 -2.970 -2.350 -2.500 -1.670 -1.640 -1.640

-1.2500 -0.9500 -I. 7006 -2.0250 -3.2500 -1.6810 -1.3209 -1.7512 -2.5614 -4.1452 -5.2391 -4.8167 -3.1094 -2.4330 -1.8853 -0.5929 -1.5482 -1.5891

1406.59 1450.150 1456.44 1484.595 1827.21 1796.731 1817.55 1898.650 1925.00 1818.237 1875.15 1606.706 1767.88 1624.321 1625.22 1590.245 1903.47 1897.321 1956.00 1952.254 1593.91 1615.321 1814.29 1900.236 1738.46 1722.365 1812.89 1916.235 1569.10 1654.367 934.4 7 980.324 -168.31 -179.325 -168.31 -179325

NilmbellZClle + Melhy/ alcoho/ + Carboll lelrach/oride

0.5500 0.3900 0.3000 0.2890 0.2980

0.6019 0.3632 02263 0.1631 0.1412

-0.2870 -0.2762 -0.4502 -0.4412 -0.5424 -0.5063 -0.5560 -0.5621 -0.5495 -0.5532

67.329 59.924 54.802 53.449 52.552

-18.600 -17.835 -1435.97 -1014.780 -21.200 -19.233 -2374.83 -2009.587 -22.000 -22.437 -3061. II -2853.841 -19.500 -22.810 -3040.90 -3371.204 -16.900 -18.845 -2845.48 -3497.399

COllld

Table I- Densities, viscosities. viscosity deviations :tndthermodynalllie excess properties or ternary liquid mixtures ,It 298.15 K- Co/l/{I

P -3

g eln . 11 mPa.s

llGrun L'.¹1 mPa.s

L'.11* V V'" V"'*

mPa.s clll' mol-¹ em'11101-¹ em) IllOr l

L'.Cn J 11101-¹

L'.C#t'*

J mol-I

Nilrube/l~e/le + Melliyl alcoliol + Car!Jo/llelmch!oride (co/lld) 0.2253

0.2465 0.2658 0.2956 0.3408 0.4094 0.46S I 0.5337 0.6457 0.6903 0.7854 0.8341 0.8341

0.5706 0.6236 0.6717 0.6734 0.6268 0.5183 0.4556 0.3856 0.2179 0.2183 0.1168 0.1173 0.1173

0.2041 0.1299 0.0625 0.0310 0.0325 0.0723 0.0763 0.0807 0.1364 0.0914 0.0978 0.0486 0.0-186

1.6240 1.5429 1.5910 1.5606 1.3700 1.5223 1.4140 1.4320 1.4430 1.4403 1.4541 1.3436 1.3436

0.2870 0.3987 0.4429 0.5362 0.4954 0.5980 0.6890 0.6980 0.6580 0.8900 1.2000 1.3527 1.3527

0.1489 0.1894 0.2866 0.5028 0.7138 0.7339 0.4905 0.4985 0.5218 0.4729 0.6786 0.9147 1.2183

-0.5620 -0.6952

-0.4523 -0.5257 -0.4100 -0.2183 -0.3400 -0.0020 -0.0257 -0.0250 -0.4127 -0.4256 -0.3862 -0.3752 -0.4493 -0.4521 -0.6260 -0.6277 -0.4295 -0.4080 -0.2240 -0.2345 -0.1 100 -0.0370 -0.1 100 -0.3800

47.669 45.569 40.138 40.199 48.933 51.324 59.379 63.179 74.466 73.620 79.416 84.787 84.787

-18.600 -18.413 -3038.46 -3167.057 -17.800 -15.393 -2190.08 -2355.685 -20.600 -18.784 -2123.94 -1079.808 -20.600 -19.524 -1687.37 -398.254 -14.767 -13.212 -175.33 -334.036 -18.900 -17.215 -1509.36 -1450.321 -14.723 -16.541 -1096.29 -1552.441 -15.253 -17.214 -1254.98 -1583.745 -14.097 -18.154 -1739.72 -1852.580 -15.158 -15.771 -1087.76 -1152.950 -15.640 -14.236 -M7.70 -527.291

-10.500 -9.357 -268.49 -9.1 SO

-10.500 -9.357 -268.49 -9.150

Nilrobe/l~e/le + Melliyl alcollOl + IA-Dioxa/le 0.0764

0.1102 0.1406 0.1691 0.1956 0.2196 0.2425 0.2637 0.2944 0.3393 0.4057 0.4637 0.5283 0.6345 0.6825 0.7758 0.8286

0.1939 0.2785 0.3565 0.4280 0.4943 0.5562 0.6135 0.6665 0.6705 0.6240 0.5136 0.4512 0.3817 0.2141 0.2158 0.1154 0.1165

0.7297 0.6113 0.5029 0.4029 0.3101 0.2242 0.1440 0.0698 0.0351 0.0368 0.0807 0.0851 0.0900 0.1514 0.1018 0.1088 0.0549

1.1860 1.2140 1.2380 1.2650 1.2800 1.3030 1.3200 1.3220 1.:1300 1.3700 1.4000 1.4140 1.3998 1.3839 1.3769 1.3601 1.3571

1.1089 1.0976 1.0683 1.1000 I. 1500 1.1200 1.1 564 1.1480 1.1577 1.2902 1.4000 1.5600 1.7500 2.2600 2.0250 2.0927 1.8426

1.1162 1.3336 1.6428 1.9514 2.1771 2.2346 2.0882 1.7825 1.3936 1.2519 1.3838 2.0235 2.2648 2.4874 3.1584 2.6614 2.4476

0.1120 0.1236 0.1 159 0.1670 0.2349 0.2221 0.2740 0.2800 0.2739 0.3570 0.37:-1 0.4683 0.5861 0.9506 0.6886 0.6520 0.3720

0.1251 0.1046 0.1665 0.1754 0.2277 0.2271 0.2514 0.2947 0.2992 0.3488 0.3909 0.4616 0.5860 0.8647 0.7642 0.57S1 0.4014

67.379 62.893 59.000 55.360 52.532 49.586 47.120 45.362 45.729 47.450 52.509 55.899 60.866 71.041 72.560 79.988 81.484

-I 1.425 -8.858 -12.594 -12093 -13.416 -14.124 -14.251 -15.098 -14.480 -15.224 -14.987 -14.727 -15.206 -13.888 -14.886 -12.912 -14.840 -13.090 -15.993 -14.430 -I 7.069 -I 7.40 I -17.487 -18.598 -16.760 -19.254 -16.000 -17.874 -15.200 -16.535 -13.890 -10.6-12 -13.210 -11.325

78.36 126.00 126.00 248.15 421.71 :'\91.62 511.10 551.67 559.98 691.23 660.30 TO.36

<)38.93

80.650 128.365 129.5-17 25-1.650 524.325 415.369 68-1.452 590.680 6-11.960 525.899 612.850 810.369 840.365 1216.04 1352.542

<)23.40 990.255 753.72 85-1.51-1 402.02 450.36-1 L'.11*, V^E* and L'.G#E", represent predicted values by Cibulka's equation

1.40r - - - ,

1.30

1.20

M

'E 1.10 u

.::! E ^1.00

a.

0.90

0.80

~

^{o 0}

o 0 0 0

//

o

0.70 t---.---,r---..---~---l

0.0 0.2 0.6 0.8

Fig. I- Variation or p with .\1 or nitrobenzene in ternary liquid l11ixture or nitrobenzene + methyl alcohol + benzene at 298.15 K.

... (2)

where

V;

represents th e molar volume and

Xi

th e mole fra ction of the ith component. The quantity V , refers to the molar volume of the mi xture which can be ca lcul ated from th e mixture density (p), and th e co mponent molecular weight Mi as below

/I

V= L,,r iM/P

^{... (3)}

i=1

... (4)

OTES

2653

Table 2 - Densities. viscosities, viscosity deviation and excess propertics of binary liquid mixtures at 298.15 K

X, Xl P ^{11 [111 V VI:: LIc#J::}

-1

g cm . mPa.s mPa.s cmJ.mol-¹ cmJ.mol-¹ J mol-I

Ni/robell:elle + Me/lty/ a/colto/

0.0000 1.0000 0.7881 0.5482 0.0000 40.6547 0.0000 0.00

0.0420 0.9580 0.8608 0.6159 0.0224 41.6663 -1.6002 142.02

0.0897 0.9103 0.9658 0.7208 0.0758 41.6328 -4.6000 294.00

0.1450 0.8550 1.0653 0.114110 0.1432 42.4715 -7.2001 472.68

0.2086 0.7914 1.1694 0.9705 0.1970 43.6453 -9.9813 558.20

0.2832 0.7168 1.2125 1.0711 0.2171 47.6945 -10.5712 651.30

0.3720 0.6280 1.2587 1.2300 0.2800 52.3705 -11.4172 784.20

0.4799 0.5201 1.3141 1.3869 0.3204 57.6392 -12.8583 780.00

0.6126 0.3874 1.3158 1.5680 0.3582 66.7499 -11.9997 784.73

0.7806 0.2194 1.2892 1.6681 0.2769 79.9948 -9.2019 543.04

1.0000 0.0000 1.1971 1.6282 0.0000 102.8402 0.0000 0.00

Ni/robell:elle + Bell:clle

0.0000 1.0000 0.8650 0.5640 0.0000 90.3006 0.0000 000

0.0887 0.9113 0.9339 0.8683 0.2099 87.9121 -3.5007 753.92

0.1796 0.8204 1.0390 1.2350 0.4799 82.9527 -9.6000 1222.79

0.2737 0.7263 1.1023 1.5054 0.6501 82.0319 -11.7008 1411.34

0.3694 0.6306 1.162J 1.6903 0.7332 81.5058 -13.4269 1400.00

0.4673 0.5327 1.1936 1.8563 0.7950 83.0603 -13.1000 1390.00

0.5682 0.4318 1.2251 2.0463 0.8776 84.6259 -12.7997 1380.00

0.6723 0.3277 1.2581 2.0992 0.8197 86.1310 -12.6000 1176.53

0.7788 0.2212 1.2748 2.0527 0.6599 88.7663 -I 1.300 I 876.50

0.8874 0.1126 1.2216 1.8851 0.3767 96.6274 -4.8008 550.00

1.0000 0.0000 1.1971 1.6282 0.0000 102.8402 0.0000 0.00

MC//l"/ a/colto/ +Bell:clle

0.0000 1.0000 0.8650 0.5640 0.0000 90.3006 0.0000 0.00

0.1979 0.8021 0.9493 0.7278 0.1669 72.6757 -7.8000 507.54

0.3570 0.6430 0.9933 0.8351 0.2767 62.0768 -10.5002 7811.31

0.4878 0.5122 1.0342 0.S502 0.2939 53.7980 -12.2853 745.09

0.5971 0.4029 1.0258 0.85()7 0.3021 49.3284 -11.32R6 773.27

0.6R95 0.3105 1.0166 0.8151 0.2620 45.51162 -10.4836 641.47

0.7692 0.2308 1.0106 0.7810 0.2292 42.2271 -9.8859 507.00

0.8384 0.1616 0.9707 0.7175 0.1667 40.6768 -R.OO07 343.07

0.8990 0.1010 0.9250 O.6S96 0.1398 39.6687 -6.00Q] 306.22

0.9S23 0.0477 0.1\346 0.6003 0.OS13 41.0228 -2.0000 152.00

1.0000 0.0000 O.n81 O.54R2 0.0000 40.6.'147 0.0000 0.00

Ni/m/JclI:clIl' + TO/llclle

0.0000 1.0000 0.8582 0 . .'1229 0.0000 107.3643 0.0000 0.00

0.1037 O.R963 0.R89') 0.56::'4 -007.'1 I 107.14.'11 0.2S00 -IW.OO

0.2066 0.7934 (J.92 I I 0.6222 -0.1291 10('.9749 0 . .'14.'13 -140.0()

0.3093 06907 0.9S42 O.6R92 -0.17.'16 106.6042 0.6392 -173.95

0.4103 0.5897 0.9869 0.7610 -0.2IS4 106.2354 0.7274 -21 1.00

0510.'1 0.4895 1.0204 0.R43S -0.2437 105.7947 0.7400 -238.00

COlllff

Table 2 - Densities, vi~cositil:s, viscosity ckviation and excess properties or binary liquid Illixturl:s at 298.15 K- CO//Id

.\", Xl P 11 1',11 V V^E I1C#'"

-1

g Cill . IllPa.s I11Pa.s CI11¹.11101-¹ CI11¹.1ll01-¹ J lllol-¹

Nilrobell:elle + TO/llelle (collld)

0.6098 0.3902 1.05~1 0.9477 -0.2492 105.3255 0.7200 -229.05

0.7094 0.2906 1.0886 1.0635 -0.2435 104.8249 0.6700 -22H6

,

0.8071 0.1929 I.lnH 1.2150 -0.2000 104.2315 0.51H6 -172.63

0.9039 0.0961 1.1601 1.4320 -0.0900 103.5550 0.2800 -41.50

1.0000 0.0000 1.1971 1.6282 0.0000 102.8402 0.0000 0.00

Melhd a/coho/+ TO/llelle

0.0000 1.0000 0.H582 0.5229 0.0000 107.3643 0.0000 0.00

0.2269 0.7731 0.8455 0.4483 -0.OH04 92.8476 0.6197 -226.00

0.3977 0.602 0.H357 0.4159 -0.1170 81.6539 0.8200 -340.7H

0.5309 0.4691 0.H275 0.4113 -0.1250 72.7882 0.8400 ^-3~8.31

0.6377 0.3623 0.820 I 0.4185 -0.1205 65.6227 0.7991 -317.00

0.7252 0.2748 0.H130 0.4363 -0.1050 59.7256 0.7391 -246.05

0.79H3 0.2017 0.80S~ 0.4562 -0.0869 54.6300 0.5200 -IS8.00

0.8606 0.1394 O.S025 0.4771 -0.0676 50.3631 0.4091 -135.00

0.9136 0.0864 0.7973 0.4928 -0.0532 46.6975 0.2791 -120.57

0.9597 0.0~03 0.7922 0.5171 -0.0300 43.5023 0.1592 -70.1 H

1.0000 0.0000 0.7881 0.54S2 0.0000 40.6547 0.0000 0.00

Nilrobell:elle + Carboll lelmch/oride

0.0000 1.0000 1.5775 0.8300 0.0000 97.5087 0.0000 0.00

0.0951 0.9049 1.3817 n.7335 -0.1724 109.2158 I 1.200 I -200.00

0.1913 0.8087 1.2025 0.6476 -0.3351 I 23. 028 S 24.5002 -390.00

0.2891 0.7109 I. 1085 0.6350 -0.4257 130.7508 31.700S -~65.16

0.3H75 0.6125 1.0369 0.6294 -0.5099 136.8747 37.3000 -552.52

0.4865 0.5135 1.0219 0.6928 -0.5255 135.9025 35.8000 -510.00

0.5871 0.4129 1.0056 0.7527 -0.5459 135.038S 34.4000 -501.52

0.6886 0.3114 1.0 II~ 0.8480 -0.5316 131.1799 29.9999 -~60.00

0.7915 0.2085 1.0317 1.0096 -0.4522 125.5286 23.8000 -320.00

0.8947 0.1053 1.09S8 1.2641 -0.2800 114.9788 12.7000 -163.77

1.0000 0.0000 1.1971 1.6282 0.0000 102.8402 0.0000 0.00

Mel/ll'/ a/coho/ + Carboll lelmcil/llride

0.0000 1.0000 1.5775 O.lOOO 0.0000 97.5087 0.0000 0.00

0.210~ 0.7896 1.6363 0.S395 0.0688 78.3466 -7.2000 161.00

0.3750 0.6250 1.6365 0.8288 0.1045 66.08S5 -10.1000 235.00

0.5069 0.4931 1.6103 0.8105 0.1234 57.1894 -11.5000 243.00

0.6154 0.3846 1.5075 0.7666 0.1100 52.3211 -10.1997 231.0 I

0.7057 0.2943 1.4297 0.7387 0.1075 47.4769 -9.9100 186.00

0.7826 0.2174 1.3205 0.7057 0.0962 44.3142 -8.7006 147.00

0.8483 0.1517 1.2271 0.6886 0.0976 41.1659 -8.1136 113.00

0.9057 0.0943 1.0877 0.6477 0.0729 40.0161 -6.0000 74.00

0.9555 0.0445 0.9051 0.5806 0.0199 41.3847 -1.8000 45.00

1.0000 0.0000 0.7881 0.5482 0.0000 40.6547 0.0000 0.00

Nilrobell:elle + /A-Dio.wlle

0.0000 1.0000 1.0195 1.0500 0.0000 86.4247 0.0000 0.00

0.0852 0.9148 1.0209 0.9093 -0.1900 89.2239 1.4006 -413.89

0.1732 0.8268 1.0273 O.n02 -0.3700 91.6679 2.4000 -867.64

0.2650 0.7350 1.03H5 0.7312 -0.4720 93.7748 3.0000 -1115.51

COllId

NOTES

2655

Table 2 - Densities. viscosities, viscosity deviation and excess properties of binary liquid mixtures at 298.15 K- Cullld

XI X2 P 11 1':.11 ^{V VI, dC#E}

-

,

mPa.s Il1Pa.s cll1'.ll1ol-¹ cll1^Jmol-¹ J mol-I g cln -

Nilrubell~el/e + 1.4-Dio.wl/e (collld)

0.3592 0.6408 1.0518 0.6294 -0.6283 95.7213 3.400 I -1586.86

0.4563 0.5437 1.0621 0.6628 -0.6510 97.995 I 4.0800 -1547.23

0.5574 0.4426 1.0799 0.6632 -0.7091 99.6547 4.0800 -1659.80

0.6625 0.3375 1.1014 0.7536 -0.6795 101.050 I 3.7501 -146-L92

0.7711 0.2289 1.1283 0.8682 -0.6276 102.0127 2.9300 -1251.65

0.8829 0.1171 1.1618 1.1409 -0.4196 102.4379 1.5200 -725.48

I .0000 0.0000 1.1971 1.6282 0.0000 102.8402 0.0000 0.00

Melhyl alwho/ + 1.4-Dio.wl/e

0.0000 1.0000 1.0195 1.0500

0.1911 0.8089 1.0843 1.0269

0.3470 0.6530 1.1228 0.9980

0.4767 0.5233 1.1324 0.9857

0.5864 0.4136 1.1049 0.9327

0.6799 0.3201 1.0703 0.8558

0.7612 0.2388 1.0569 0.808~

0.8323 0.1677 0.9860 0.7:\04

0.8950 0.1050 0.9351 0.6788

0.9502 0.0~98 0.8468 0.5806

1.0000 0.0000 0.7881 0.5482

The v iscosit y deviations (L'lll), the excess molar vo lumes

(VT:)

and the excess Gibbs free energies of activation of viscous flow

(ddT:)

for the ternary mixtures have been fitted to C ibulka's eq uation (Eq.5).

...

(5) where

... (6) The function y

_ij^E

(for ij binary mixtures) is giv en by Redlich-Kister's equation (Eq. 7):

"

Y;j'"

= X;Xj

L. !\p

^{(x; - .r}j ) " ... (7)

,,=0

where Y

i/ '

is L'l ll

or

v': or L'lC # l ,

^x;

denotes th

e mole

fractio n of compo nent i of the ij mixture with xF I -x;, and

Ap are the adjustable parameters.

In order to obtai n the va lue of yE (v ide Eq. 6) the experim ental va lues of L'lll ,

VI, and !1C^IlC

are required for th e follow ing binary mixtures nitrobenzene ( I ) + meth yl alcohol (2); nitrobe nzene ( I ) + benzene

(3);

methyl alcohol (2) + benzene

(3);

nit robenzene ( I ) + toluene

(3);

methyl alcohol (2) +tol uene

(3);

nitroben-

0.0000 86.4247 0.0000 0.00

0.0728 71.3772 -6.3009 138.10

0.1221 61.1424 -9.4001 227.69

0.1749 54.2062 -10.4000 352.02

0.1770 49.9857 -9.5995 396.60

0.1470 46.7061 -8.5996 339.54

0.1404 42.9843 -8.6003 274.30

0.0980 42.0304 -6.3000 213.57

0.0779 40.5605 -4.9001 161.16

0.0074 41.1341 -1.8000 -1.90

0.0000 40.6547 0.0000 0.00

ze ne ( I ) + carb on tetrachloride (3); methyl alcohol

(2)

+carbon tetrachl oride

(3);

nitrobenzene ( I ) + 1,4-di- oxane (3); methyl alcohol (2) + 1,4 dioxane (3).

The experim ental values of L'lll ,

^VC

and

dCIi/::

(Tab

le 2) of the above binary mixtures

were fitted in

th e Redli ch-Ki

ster's

polynomial Eq

.

(7) to obtain the valu es of adjustable parameters

Ap. The

coeffic ient in Eq.7 along with the stand ard deviation (0) have been prese nted in Table 3. Using these calculated value. of Ap, th e va lues of y E12, y EI3 and yEn have been ob tain ed from Eq. 7. Hav in g thus ob tained the val ues of y '\ill, the experim ental valu es of L'lll,

V^lo'

and

L1C^ilE

for ternary mixtures were fitted to Cibulka's equation

(E

q. 5) to obta in the values of coefficients B

I ,

B 2 and B, by th

e

method of least

squares.

After having determined the va lues o f coefficients B

I,

B2 and B,.

the theoretical (ca lculated) va lues of L'lll ,

VI:

and

!1C^IlI::

for ternary mixtures have been ob tain

ed

from Eq. 5.

The standard deviation in regard to ex perimental and theoretical va lues of L'lll , VI: and

dCIiE for

the ternary mixtures was obtained uSing the foll owing expres-

. 1 2 sion .

O'(Y E) = ^{L(Ycxpll - Ycalc )}

[

E E

2] 1 12

(1/ - p)

..

. (8)

Table:\ - Coefficients of Redlich-Kister's Equation and the corresponding standard deviation (0 for the bin:1ry mixtures at 298.15 K Viscosity deviations (611) and

excess functions (yE)

611 (mPa.s) 0(cm³ mor^l)

6G#E(J mor^l)

611 (mPa.s) 0(cm³ mor^l) 6C#E(J mol-I)

611 (mPa.:;) 0(cm³ mor^l)

6C#E(J mor^l)

611 (mPa.s) 1;E(c1113 mor^l) 6C#E(J mor I)

611 (mPa.s)

liE (CI11' 11101-1) 6c#E(J 11101-¹)

611 (mPa.s)

o

^{(C1113 morl)}

6C#E(J mol·^l)

611 (mPa.:;) VE _(cm) mol-I) 6C#E(J 11101-¹)

611 (mPa.s) 0(Cm³1110rl

) 6C#E(J mor^l)

611 (mPa.s) It' (CI11' 11101-1

) 6C#E(J mor^l)

A.I A~ o

Nilrobell~elle+Melliyl alcoliol

1.330 0.498 0.143 0.005

50.320 -0.964 12.133 0.059

29H9.8 -3319.2 2814.0 69069.4 101175.7 -134372.6 -340641.5 -169098.0 0.825

1.205 46.913 2999.5

3.392 55.194 5597.1

-0.492 3.017 -933.3

-0.492 3.433 -1410.1

0.161 5.356 593.8

0.636 -0.451

192.0

-0.011 0.163 -166.2

-0.076 -0.021

196.1

Nilrobell~elle + Bell:elle -0.035

15.078

5685.8 -16483.4 -24852.7 52673.1 23887.9 42066.7 Melliyl alcoliol +Bell~elle

0.194 8.553

5685.8 -19677.9 3744.3 46618.0 -4177.534260.1

Nilrobell~elle + Toillelle -0.010

0.408

-340.2 -1923.9 -2903.1 Melliyl alcoliol+ Toillelle

-0.066 0.174

5798.1 4033.9 -2219.9

0.012 0.096 0.475

0.003 0.011 0.364

0.0026 0.0282 0.388

0.0042 0.0123 -340.2 -2487.1 13563.0 807.3 -34693.6 22176.5 0.646 Nilrobellzelle + Carboll lelrachloride

-2.169 0.021 -0.495 147.620 -13.183 -5.347

-2075.9 897.6 -718.5 -9661.3

0.0118 0.0135 7285.3 36611.9 -6594.1 -35677.0 0.476 Melliyl alcoliol + Carboll tetrachloride

0.452 -43.086

965.4

-2.748 16.121 -6537.6

0.684 -40.348

1459.9

0.145 -7.482 484.3

-0.905 0.499 937.1

0.227 -18.715

-718.5 -9807.2 20086.9 13443.7 -54703.0 31980.9 Nitrobellzelle + 1,4-Diox(/lle

0.0111 0.0167 0.995

-0.90 I 0.0050

(U55 0.0185

700.5 -17927.0 3612.2 50733.2 -4279.1 -42964.1 0.941 Metliyl (/Icoliol + 1.4-Dioxalle

0.229 -2.246 1016.2

-0.282 -8.854 700.5

D.O 140 0.0235 -2300.6 -30282.4 32793.6 69975.7 -7 289.9 0.993

where

yE

is

Llll

or V^E or i1C^IlE, n is the number of experimental data and p is the number of parameters in Cibulka's equation. The values of coefficients 81,

8₂, 8₃ and

CJ(Ll1l)/CJ(VO)/o(LlC#E)

have been presented in Table 4.

It

is seen that the experimental values of Lll1 or V^E or i1C^llto' for the ternary mixtures compare fairly well with those predicted by Cibulka's equation.

A perusal of values of

Llll

(Table I) in respect of ternary liquid mixtures shows that these are positive over the entire range of composition except for the ternary mixture: nitrobenzene

+

methyl alcohol

+

carbon tetrachloride, for which

Llll

^tS negative. The positive values of

Llll

and i1C^IlE in the case of ternary mixtures of nitrobenzene

+

methyl alcohol

+

(benzene;

+

toluene;

+

1,4-dioxane) indicate that the

NOTES

2657

Table 4 - Coerticients of Cibulka e:quation and the corresponding standard deviation (a) for the ternary mixtures at 298.15 K Viscosity deviations (1l11)

and excess functions (yE)

13., a

Ni/robell;elle+ Me/hd IIlcollOl + !Jell;elle

1111 (mPa.s) -17.316

161.052 -42755.7

-12.911 14.762

27.026 10356.6

0.073 0.027 0.8-1

\1' (Clll' mOrl) IlC#E(J morl)

-402.217 36X23.6

Ni/robell;elle + Me/hyl alcohol + Toluene 1111 (mPa.s)

V '

(cm' morl) IlC#I'(J mol'l)

18.473 -545.530 100-151.930

30.647 3-17.563 IX3444.685

-5.956 1282.006 -153399.432

0.197 0.035 0.256 Ni/robell;clle + Mc/hd alcohol + Carbon /e/mch/oride

1111 (mPa.s)

V :

^{(cm' mor l)}

IlC#E(J mor I)

-5.437 -1556.720 -IOR360.092

-30.523 23.586 -IORI~U37

-26.40 I 1863.509 -20922.189

0.012 0.047 0.311 Ni/robell;elle + Me/hd alcollOl + 1,4-Dioxllne

1111 (lllPa.s)

v:

^{(cnl"' 1l10rl)}

IlC#E(J mol'l)

9.830 -357.487

68.172 -312.519

-33.151 571.215 181009.565

0.015 0.036 0.936 -18108.263 -195217.IX3

fl ow o f these mixtures is difficult as co mpared with the behavi our o f pure liquid

s.

On th e other hand, the nega tive valu

es

of t.1l and

!JelIE

obse rved for the ternary mixture nitrobenzene + meth y l alcohol + carb on tetrachl

oride

indicate th e

easier fl

ow or thi s mi

x

ture compared w ith th e behaviour of th e pure liquid s. Th ese conclu

si

ons are borne out by the vi

ews

recently report ed by Domingue

z ef al.I~.I'\

Th e values of

VI:"

(Tabl

e

I ) for all th e ternary mixtures und er di

scussion

arc negati ve over th e entire range of compos ition. The nega ti ve values or v/" may be auri butedl

-l

to intermolecular di polar interacti ons and geometri

ca

l fitting betwee n mi xing components in th e ternary mixtures,

The plots

or t.11, V^E

and

!Jelll:"

versus

.\"1

for th

e

binary mixtures are parabolic in

shape and are charac-

teri

zed by th

e presence o f w

ell-defined

maximal minima which indi cate th

e

presence of complex formation

².15

betwee n th e mi x ing components of binary mi x tures. The interacti ons in a ternary i + j + k mixture are closely dependent l

(, on the interacti

ons in the constitu

ent i + j , j+k and

i + k binary mixtures. It

should thererore be poss

ible to correlate th e nature o f interactions occurring in ternary mixtures with those

of

binary mixtures. From th

e

fact th at th e binary mix tures arc characte ri

zed

by co mplex formation between their constitu

ent

components, it follows that the parabolic

shape o

f the plots o f t.1l

, V/·: and !JellE

versus

XI

indicates that int era cti

ons occ

urrin

g

in the ternary mixtures of the titl e study are of

spec

ific nature.

References

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2 Maheshwari G & Singh M . ./ Illdillll Chelll Soc, 79 (2002) 659.

3 Vogel A I. II Tex/ Book lij" PJ"(IClical Organic Chelllis/!"\". 5th Edn, (John Wiley. New York) 1989.

-I Ridlich J A. Bunger W 13 & Sokano T K. Techniques III Chelllis/ry, Vol 2, Organic So/l'en/s, 4th Edn .. (John Wiley, New York) 1986.

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6 Singh M. Gupta PC & Kesharwani R N . ./ Chelll Eng Da/({, 40 (1995) 35X.

7 Swain N. ChakJ"avorlty V, Singh S K & Panda D. Indilll/ ./

Ch elll , 38A (1999) I 16.

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