J. Pure Appl. Ultrason. 27 (2005) pp.

61-69

Ultrasonic velocity, viscosity and density studies of poly (ethylene glycols)(PEG - 8,000, PEG - 20,000) in acetonitrile (AN) and water (H2O) mixtures at 250C
V.K. SYAL, ANITA CHAUHAN and SUVARCHA CHAUHAN Deptt. of Chemistry, Himachal Pradesh University, Summer Hill, Shimla 171 005

Ultrasonic velocity, viscosity and density studies on solutions of PEG's of molecular weights (8,000 - 11,000) and (20,000) have been carried out in water (H2O) and its binary mixtures with Acetonitrile (AN) at 250C. From the velocity, density and viscosity data values, various acoustical parameters namely, specific acoustic impedance (Z), adiabatic compressibilty (), intermolecular free length (Lf), relative association (R.A.), molar sound velocity (R), Wada's constant (W), solvation number (Sn), apparent molar adiabatic compressibilty (ks), viscous relaxation time (), internal pressure () and free volume (Vf) have been calculated. All these parameters have been discussed separately to throw light on the polymer - polymer and polymer - solvent interactions.

INTRODUCTION Poly (ethyleneglycols), HO (CH2 CH2O)n H, n 4 have variety of applications in pharmaceutical preparations, cosmetics and in the metal casting proces1. Acoustical properties of polymer solutions have shown that ultrasonic velocity and its derived parameters provide much information on molecular interactions, which are of utmost importance for processes involving polymer production and their uses.2 Very few reports are there in the literature on the ultrasonic studies of PEG's solutions in binary aqueous + non - aqueous solvent systems. Therefore, in the present investigation, ultrasonic velocities, densities and viscosities of PEG's of (Mol. Wt. 8,000-11,000 and 20,000) in water and its binary mixtures with AN containing AN at 20 mole % intervals have been carried out. Various derived parameters such as specific acoustic impedence (Z), adiabatic compressibility (), intermolecular free length (L f ), relative association (R.A.), molar sound velocity (R), J. Pure Appl. Ultrason. Vol. 27 No. 2 & 3 (2005)

Wada's constant (W), solvation number (S n ), apparent molar adiabatic compressibilty (ks), viscous relaxation time (), internal pressure () and free volume (V f ) have been evaluated from ultrasonic velocity and density data and have been discussed in terms of polymer - polymer and polymer - solvent interactions. Experimental Water required for the calibration of the viscometer, pycnometer and ultrasonic velocity liquid cell was twice distilled over acidified KMnO4 through a 750 mm long vertical fractionating column. Middle fraction of about 800 - 1000 ml was collected and stored in coloured bottles for use. The conductivity of distilled water was found to be 1-2x10-6 ohm-1cm-1. The ultrasonic velocity of this conductivity water has been found to be 1500 m / s at 250 C at 1 MHz, which agreed well with the literature value3. Acetonitrile (AN) (Analar of 99% purity, Sisco 61

Research Laboratories, Pvt. Ltd. Mumbai) was purified by the method reported earlier 4 . The purified solvent AN with specific conductance (1 4) x 10-8 ohm -1 cm -1, density 0.7761 gm /cm3 ( 0.7766 gm/cm 3 ) 5 and viscosity 0.3419 CP (0.341CP) 5 all at 250C was used for the present measurements. The physical constants of the above purified AN were found in agreement to the corresponding literature values given above in brackets. Density measurements were carried out with a precision of 0.01% using sealable pycnometer of capacity 25 cm3, of pure solvents, solvent mixtures as well as of solute solutions in a water thermostat, whose temperature was kept constant within the range of 0.05%. Viscosity measurements were carried out with a precision of 0.2% using calibrated Ubbelhode suspended bulb level viscometer, whose flow time for doubly distilled water was found to be 375 seconds at 250 C. Ultrasonic velocity measurements were carried out at 1 MHz using interferometer supplied by Mittal Enterprises, which is a direct and simple device for measuring of sound velocity in liquids. Polymers, Poly (ethyleneglycol) (Mol. Wt. 8,000 - 11,000, s.d. fine- Chem Ltd. Mumbai) and, Poly (ethyleneglycol) (Mol. Wt. 20,000, Sisco Research Laboratories Pvt. Ltd. Mumbai) were used as such after drying for few hours in vacuum. The different compositions of AN and water mixtures having 0,20,40,60,80 and 100 mole % of AN were prepared by volume using the following equation :Composition of solvent mixture (Sm) = XAMA /A + XBMB / B where, XA and XB are the mole fractions, MA and MB are the molecular weights and A and B are the densities of solvents A and B respectively. A series of solutions of polymers of different molecular weights have been prepared by dissolving a known weight of that polymer to a fixed volume of solvent / solvent mixtures and then stirring until a clear solution is obtained. The solutions were filtered by using Whatmann filter paper. 62

RESULTS AND DISCUSSION Various derived acoustical parameters of PEG's in AN - H 2 O solvent system have been calculated by using the equations as reported in literature earlier 6,7,8. The measured and derived acoustical parameters have been presented in Table 1. It is clear from Table 1, that density values decrease regularly with increase of AN content in AN + water mixtures. Also, the densities of PEG's increase with increase in concentration of PEG in all the studied mixtures. Ultrasonic velocity (U) values tend to increase with the increase of concentration of PEG's in various solvent mixtures. This suggests that disruption of water structure is enhanced further with the addition of PEG. Similar increase in velocity with increase of concentration of cellulose acetate has also been reported in cyclohexane and carbon tetrachloride by Rajagopalan et .al 9 and for PEG in DMSO +H2O system by Srilalitha et.al 7. In pure solvent system, velocity values tend to decrease with the increase of AN content in AN + H2O solvent mixtures. The specific acoustic impedence (Z) values have been presented in Table 1. From the Table 1 , it is evident that Z values increase with increase in concentration of polymer in water, AN and in all the studied composition range at 250C. This is in agreement with the theoretical requirements as U and both increase with increase of concentration of solute. The increase of Z values with solute concentration can be attributed to the effective solute-solvent interactions. A similar type of behaviour has been obtained for tetraalkylammonium and alkali metal salts in methanol + chlorobenzene mixtures by Syal et. al10. There is a decrease in Z values with increase in AN content in AN+ water solvent system for both the polymers, which is in accordance with decrease in U and values with increase in AN content in the mixture. Similar decrease has been reported11,12 in case of PVP and PVA in DMSO+H 2 O solvent system. From Table 1, it is evident that, adiabatic compressibilty () values of polymer solutions show increase with the increase of AN to AN + H 2 O solvent system which shows that AN J. Pure Appl. Ultrason. Vol. 27 No. 2 & 3 (2005)

Table 1. Wt %, W %, density (), ultrasonic velocity (U), adiabatic compressibilty (), specific acoustic impedance (Z), intermolecular free length (Lf), relative association (R.A.), molar sound velocity (R), Wadas constant (W), solvation number (S n) and apparent molar adiabatic compressibility (ks) of PEG of molecular weight (8000 11,000) in 100 mol% H2O and 20, 40, 60, 80 and 100 mol % AN at 25oC. 100mol% H2O W % 0.0 0.5 1.0 1.5 2.0 3.0 0.0 0.5 1.0 1.5 2.0 3.0 0.0 0.5 1.0 1.5 2.0 3.0 0.0 0.5 1.0 1.5 2.0 3.0 x 10-3 Kg m-3 0.9970 0.9975 0.9985 0.9994 1.0007 1.0020 0.9235 0.9248 0.9260 0.9271 0.9289 0.9299 0.8657 0.8672 0.8684 0.8699 0.8711 0.8735 0.8262 0.8295 0.8304 0.8311 0.8320 0.8346 U m s-1 1500.0 1508.3 1510.2 1511.6 1513.4 1517.0 1480.9 1483.6 1485.8 1487.8 1490.6 1495.0 1383.0 1387.6 1388.2 1389.2 1389.9 1391.4 1334.4 1336.8 1337.4 1338.0 1338.3 1339.8 x 1010 m2 N-1 4.4578 4.4067 4.3912 4.3791 4.3630 4.3367 4.9376 4.9127 4.8918 4.8729 4.8452 4.8115 6.0393 5.9890 5.9755 5.9566 5.9424 5.9133 6.7974 6.7461 6.7327 6.7210 6.7107 6.6749 Zx 10-6 Kg m-2 s-1 1.4955 1.5045 1.5079 1.5107 1.545 1.5200 1.3676 1.3720 1.3759 1.3793 1.3846 1.3902 1.1973 1.2033 1.2055 1.2085 1.2107 1.2154 1.1025 1.1089 1.1106 1.1120 1.1135 1.1182 Lfx 1011 m 4.3427 4.3177 4.3101 4.3042 4.2962 4.2833 4.5704 4.5588 4.5491 4.5403 4.5274 4.5116 5.0546 5.0335 5.0279 5.0199 5.0139 5.0016 5.3625 5.3422 5.3369 5.3323 5.3282 5.3139 R.A. 1 0.9986 0.9992 0.9998 1.0007 1.0012 1 1.0007 1.0016 1.0023 1.0036 1.0037 1 1.0006 1.0018 1.0033 1.0045 1.0069 1 1.0034 1.0043 1.0050 1.0060 1.0088 Rx 102 20.69 20.68 20.67 20.65 20.64 20.63 25.03 25.01 24.96 24.94 24.93 24.91 29.87 29.85 29.82 29.77 29.74 29.66 36.17 36.05 36.02 35.99 35.95 35.85 Wx1011/7 14.58 14.60 14.59 14.58 14.57 14.56 17.47 17.46 17.45 17.45 17.42 17.42 20.74 20.74 20.73 20.72 20.68 20.62 24.98 24.92 24.89 24.88 24.86 24.80 m10/3 s-1/3 M19/7 N1/7 Sn x 10-2
___

J. Pure Appl. Ultrason. Vol. 27 No. 2 & 3 (2005) 63

Ksx 1010 m4 s2 kg-1 22.35 21.98 21.92 21.85 21.74 21.59 26.73 26.56 26.35 26.22 26.01 25.81 34.88 34.39 34.31 34.15 34.03 33.81 41.14 40.47 40.42 40.34 40.25 39.92 Cont...

6.63 4.11 3.22 2.89 2.44 ___ 2.47 2.26 2.12 2.26 2.04 ___ 3.57 2.25 1.94 1.69 1.45 ___ 2.76 1.74 1.35 1.15 1.07

20mol % AN

40mol % AN

60mol % AN

1 1.0022 1.0037 1.0075 1.0078 1.011

1 1.0022 1.0046 1.0059 1.0070 1.0116

depolymerized water and there is evidence in literature that AN acts as breaker for structure 4 and therefore compressibility increases with increase of AN content . However the values tend to decrease with the increase of PEG's concentration. This can be explained in terms of the electrostatic effects of polymer on the surrounding solvent molecules. It has been proposed by Kalyanasundaram et.al 13 that solvent molecules are entrapped in voids formed during uncoiling of polymer chains in solution and there exists electrostatic attraction between these molecules and polymer chain which results into relatively incompressible solution with increase in AN content in solvent mixture. This supports the solvation of polymer which results into relatively incompressible region due to attractive interactions at the oxygen sites of PEG with water dipoles 7. The increasing trend in values with the increase of AN to AN + water solvent mixture is in contrast to the behaviour observed in dioxane + AN mixtures for tetraalkylammonium salts by Syal and co-workers 14 . With increase of AN content in AN + water solvent system, Lf values show an increasing trend. However, with increase in concentration of polymers, L f values decrease in a slightly curvilinear manner. This is in agreement with the observations made by Syal et. al. 15 for alkali bromides in DMSO + Dioxane solvent mixtures. The decrease of Lf with concentration suggests the presence of strong solute - solvent interactions. A similar type of behaviour has also been reported by Kalyanasundaram and co-workers 16 in the ultrasonic velocity studies on Poly (methylacrylate) (PMMA) in DMF solutions at different temperatures. The relative association (R.A.) values show slight increase with the increase of AN content in AN + water mixtures. Also, the values of R.A. do not vary much from the value of unity as we move from pure water to 100 mole% AN. However, R.A. values increase with increase of solute concentration in all the studied mixtures. This increase is again due to the fact that polymer solvent interactions dominate over solvent solvent interactions is true for both Poly (ethyleneglycols) of different molecular weights. A similar increase in the value of R.A. has been J. Pure Appl. Ultrason. Vol. 27 No. 2 & 3 (2005)

Ksx 1010 m4 s2 kg-1

46.62 46.23 45.96 45.55 45.45 45.01 ___ 1.09 1.08 1.21 1.05 1.02 30.77 30.72 30.67 30.57 30.57 30.48 44.72 44.62 44.55 44.38 44.36 44.23 5.6081 5.5980 5.5880 5.5742 5.5686 5.5509 1.0357 1.0388 1.0416 1.0462 1.0476 1.0528 7.4343 7.4075 7.3811 7.3447 7.3300 7.2836 1298.8 1299.6 1300.7 1301.4 1302.3 1304.1 0.7974 0.7993 0.8008 0.8039 0.8044 0.8073 0.0 0.5 1.0 1.5 2.0 3.0 100mol % AN

Sn x 10-2

m10/3 s-1/3 M19/7 N1/7

Wx1011/7

Rx 102

Lfx 1011 m

R.A.

Zx 10-6 Kg m-2 s-1

x 1010 m2 N-1

x 10-3 Kg m-3

Table 1 Contd...

80mol% H2O

W% %

64

0.0 0.5 1.0 1.5 2.0 3.0

0.7761 0.7780 0.7800 0.7812 0.7822 0.7861

1282.8 1283.8 1284.4 1285.0 1286.0 1287.6

U m s-1

7.8300 7.7988 7.7715 7.7523 7.7304 7.6729

0.9955 0.9988 1.0018 1.0038 1.0059 1.0121

5.7554 5.7439 5.7339 5.7268 5.7187 5.6974

57.47 57.35 57.21 57.13 57.07 56.81

39.42 39.35 39.26 39.22 39.18 39.04

__ 0.96 0.90 0.79 0.75 0.79

50.44 49.99 49.69 49.51 49.31 48.69

found in case of sucrose solution in water + AN mixtures4, however, in aqueous urea solution, there is decrease in R.A. value with increase of urea concentration17. It has been found that molar sound velocity (R) and Wada's constant (W) values insignificantly decrease with increase of concentration of solute as well as with decrease of AN content in water + AN mixtures for both polymers. This type of behaviour is similar to that observed by Syal and co-workers4 for the ultrasonic velocity measurements of sucrose in binary solvent mixtures of water + acetonitrile at 25, 35 and 450C. The calculated values of solvation number (Sn) of PEG' s in AN, H2O and various AN + water mixtures have been presented in Table 1. It is clear from this Table that Sn values in general decrease with increase of concentration of polymer and also with the increase of AN content in AN + H2 O solvent system. The change in the magnitude of Sn with solvent composition may be accounted for the decrease of dielectric constant and change in molar volume of AN and H2O molecules. It can further be inferred that in water - rich region, polymer molecules are more hydrated by water than AN, due to its smaller molar volume as compared to AN. However positive values of S n supports polymer solvent interactions18. The apparent molar adiabatic compressibility (ks) values increase with increase of AN content in AN + water mixture. However, with increase in concentration of PEG's in AN, H2O and all the studied mixtures, ks values show decreasing order. Apparent molar adiabatic compressibilty (ks) has been plotted against the square root of concentration (C) according to Masson's equation

170 160 150 140 130 120 110 100 90 80 70 0 0.5 1 1.5 2
0.00% 20 40 60

Fig. 1. Plot of apparent molar adiabatic compressibility (ks) versus square root of concentration (C) of PEG (Mol. Wt. = 20, 000) at different %age composition of AN in AN + H2O mixture at 250 C

as shown in Fig. 1 ks = 0ks + SkC From the linear plots, limiting molar adiabatic compressibilty (0ks) at infinite dilution and S k values have been obtained from the intercepts and slopes of the lines. These values have been presented in Table 2 for both PEG of different molecular weights. It is clear from Table 2, that 0 ks values increase with increase in AN content in AN + H2O solvent mixture. Large positive 0ks values for PEG (Mol.Wt. 20,000) than PEG (Mol. Wt 8,000 11,000), shows its dependence on the molecular weight of polymer due to extra number of monomers. Negative values for S n have been obtained, which in general increase in magnitude with the increase of AN content in AN + H2 O solvent system. Large negative 0 ks values for alkali metal salts and large positive 0ks values for

Table 2. Limiting apparent molar adiabatic compressibility (0ks) and Sk values for PEGs of different molecular weights in water, AN and AN + H2O mixtures at 25oC. Mol% AN 0 0 20 40 60 80 100 0ks x 1010 22.28 22.28 27.09 34.84 40.92 47.09 50.92 Sk x 1010 -0.38 -0.38 -0.74 -0.58 -0.53 -1.19 -1.22 0ks x 1010 90.68 90.68 108.61 141.55 166.51 189.11 204.52 Sk x 1010 -2.25 -2.25 -2.86 -3.94 -3.70 -5.01 -5.92

J. Pure Appl. Ultrason. Vol. 27 No. 2 & 3 (2005)

65

Table 3. Wt% age W%, density (), viscosity (), ultrasonic velocity (U), = - 0/0 C, viscous relaxation time (), internal pressure () and free volume (Vf) of PEG of molecular weight (8,000-11,000) in 100% H2O and 20, 40, 60, 80 and 100 mol% AN at 250C W% 0.0 0.5 1.0 1.5 2.0 3.0 20mol % AN 0.0 0.5 1.0 1.5 2.0 3.0 40 mol % AN 0.0 0.5 1.0 1.5 2.0 3.0 60mol % AN 0.0 0.5 1.0 1.5 2.0 3.0 80mol%AN 0.0 0.5 1.0 1.5 2.0 3.0 100mol % AN 0.0. 0.5 1.0 1.5 2.0 3.0 x 10-3 Kg m-3 0.9970 0.9975 0.9985 0.9994 1.0007 1.0020 0.9235 0.9248 0.9260 0.9271 0.9289 0.9299 0.8657 0.8672 0.8684 0.8699 0.8711 0.8735 0.8262 0.8295 0.8304 0.8311 0.8320 0.8346 0.7974 0.7993 0.8008 0.8039 0.8044 0.8073 0.7761 0.7780 0.7800 0.7812 0.7822 0.7861 x 10-3 Kg m-1s-1 0.8903 0.9976 1.1412 1.2732 1.4059 1.6821 0.8576 0.9468 1.0760 1.2031 1.3403 1.6363 0.6452 0.7123 0.8043 0.8948 0.9935 1.2084 0.4839 0.5371 0.5970 0.6569 0.7171 0.8624 0.3911 0.4338 0.4747 0.5206 0.5688 0.6823 0.3419 0.3890 0.4272 0.4669 0.5122 0.6102 U m s-1 1500.0 1508.3 1510.2 1511.6 1513.4 1517.0 1480.9 1483.6 1485.8 1487.8 1490.6 1495.0 1383.0 1387.6 1388.2 1389.2 1389.9 1391.4 1334.4 1336.8 1337.4 1338.0 1338.3 1339.8 1298.8 1299.6 1300.7 1301.4 1302.3 1304.1 1282.8 1283.8 1284.4 1285.0 1286.0 1287.6 = - 0/0 C ___ 0.1704 0.2818 0.3513 0.4095 0.5134 ___ 0.1470 0.2546 0.3289 0.3979 0.5242 ___ 0.1470 0.2465 0.3158 0.3817 0.5039 ___ 0.1554 0.2337 0.2919 0.3407 03.4515 ___ 0.1544 0.2137 0.2703 0.3212 0.4295 ___ 0.1948 0.2495 0.2985 0.3522 0.4531 x 108 s 52.92 58.61 66.82 74.34 81.78 97.26 56.45 62.02 70.18 78.16 86.58 93.24 51.95 56.87 64.08 71.06 78.72 95.27 43.85 48.31 53.59 58.86 64.16 76.75 38.76 42.84 46.72 50.98 55.59 66.26 35.69 40.45 44.26 48.26 52.79 62.43 x 10-8 atm 8.55 9.04 9.66 10.21 10.73 11.74 6.99 7.34 7.83 8.28 8.74 9.65 5.13 5.38 5.73 6.05 6.37 7.04 3.65 3.85 4.06 4.26 4.46 4.90 2.62 2.76 2.89 3.04 3.17 3.48 1.85 1.98 2.07 2.17 2.22 2.49 Vf x 1014 59.64 50.70 41.52 35.28 30.46 23.35 73.99 63.96 52.91 44.84 38.25 28.47 125.35 108.60 90.56 77.23 66.09 49.35 231.29 198.32 169.35 146.82 128.77 97.80 403.77 345.96 302.62 263.70 231.14 176.30 682.64 563.15 489.67 428.86 373.68 287.92

large tetra alkyl (phenyl) salts in DMF + DMSO and in AN + BN mixtures by Gill19 have been explained on the basis of solvation effect of electrolyte. Viscosity values of PEG along with its parameters have been presented in Table 3. It is 66

evident from this Table, that viscosity values increase with increase of concentration of solute in AN, H2O and all the studied compositions. Similar behaviour has been observed by Subha and coworkers20 in the study of effect of polymer and temperature on the critical micellar concentration J. Pure Appl. Ultrason. Vol. 27 No. 2 & 3 (2005)

of aqueous sodium dodecyl sulfate. The whole viscosity data in the present case has been analyzed by Jones - Dole equation as reported in literature21. The plots of against c for both PEG 's in AN, H2O and over the whole concentration range found to be linear as shown in Fig. 2 for PEG of molecular weight = 8,000-11,000. Jones - Dole viscosity A and B - coefficients at 250C have been obtained from these plots by least square method with the help of computer. Positive and constant values of B - coefficient from the present study shows the presence of solute-solvent interactions and also suggest that polymer here acts as structure maker and that there is no preferential solvation of the solute over the entire

solvent composition range as shown in Table 4. In the literature, it has also been pointed that large tetraalkylammonium halide salts show no preferential solvation in DMSO + AN, DMSO + dioxane solvent mixtures22. From the viscosity data, it is evident that viscosity of solution increases with the increase of AN content up to 20 mole % AN and then decreases with further increase of AN content thus showing the presence of strong solute - solvent interactions up to 20 mole % of AN and then decreases. Viscous relaxation time () values for both PEG's calculated by using viscosity and ultrasonic velocity data, in general, increase with increase in concentration of solute in all the studied mixtures. In pure solvent systems, values in general decrease with the increase of AN content in AN + H20 solvent system, but it shows maximum at 20 mole % AN for both PEG's of different molecular weights. The calculated values of internal pressure () for both PEG's presented in Table 3, show that these values increase with increase in concentration of solute in all the studied mixtures. The increase of with increase of concentration indicates the increase of cohesive forces, indicating that more water molecules are able to interact at the oxygen sites of PEG chains through H - bonding type of interactions 7. In pure solvent system, values tend to decrease as the AN content is increased in AN + H2O solvent system. This is true for both PEG's which again reflects that more water

Fig. 2. Plot of ( = - 0/0 (C)1/2) versus square root of concentration) (C1/2) of PEG (Mol. Wt. = 800011000) at different %age composition of AN in AN + Water solvent system at 25oC.

Table 4. Experimentally determined viscosity B (dm3 mol-1) - coefficient in AN, water and AN + H2O solvent mixtures for both PEGs of different molecular weights at 25oC. Mol% AN 0 20 40 60 80 100 PEG (8,000 - 11,000) B 0.33 0.36 0.34 0.28 0.26 0.25 PEG (20,000) B 0.53 0.53 0.49 0.53 0.52 0.49

J. Pure Appl. Ultrason. Vol. 27 No. 2 & 3 (2005)

67

3. 4.

5.

6.

Fig. 3. Plot of free volume (Vf) versus conc. of PEG (20000) upto 60 mol% of AN in AN + H2O solvent system at 25oC.

7.

molecules are set free on the addition of AN. The calculated free volume (Vf) of PEG's of different molecular weights show a decreasing order with increase in concentration of polymer as shown in Fig. 3. which is of reverse to that of values of solution in AN, H2O solvent system. This increase in and decrease in Vf with concentration of PEG suggests ordered structural arrangement in the system due to decrease in entropy. Similar trend for epoxy resins has been reported by Sanariya et.al23 on bisphenol - C. From the above studies it can be concluded that AN acts as a structure breaker in AN + H2O solvent system releasing more water dipoles to interact at oxygen sites of PEG chains. However the general behaviour of these parameters in PEG - 8000 and PEG - 20,000 is same except for small changes in magnitude in these parameters which attributed to different molecular weights. ACKNOWLEDGMENTS V. K. Syal, S. Chauhan thank UGC, New Delhi for the sanction of major research project F.12-145 /2001 (SR-1). A.C. thanks H.P.U. for the award of fellowship and UGC for the award of Project fellowship. REFERENCES
1. 2. Encyclopedia of Polymer Science and Technology; John Willey and Sons, Inc. (1996). Kalyanasundaram, S., Sundaresan, S. and Hemalatha, J., Determination of interaction

8.

9.

10.

11.

12.

13.

14.

15.

16.

17.

18.

parameter in aqueous Poly (vinylpyrrolidone) solutions, Bulletin of electrochemistry 15 (1999) 501. Pandey J. and Kumar Ashok, Ultrasonic velocity in pure liquids, J. Pure and Appl. Ultrasonics 16 (1994) 63. Syal, V. K., Chauhan, S. and Gautam, R., Ultrasonic velocity measurements of Sucrose in binary solvent mixtures of water + Acetonitrile at 25, 35 and 450 C, Ind. J. Pure Appl. Phys. 36, (1998) 108. Chauhan, S. Syal, V.K. and Chauhan, M.S., Viscosity and ultrasonic velocity studies of binary mixtures of Acetonitrile-propylene carbonate at different temperatures, Indian Journal of Pure and Appl. Phys., 32 (1994) 186. Desai, J.A. and Parsania, P.H., Ultrasonic stusies of Poly ( 1,1/ - cyclohexylidenyl - 4,4/ Diphenylene -2,4 Toluene Disulfonates) solutions at 300 C, J. Pure Appl. Ultrason. 19 (1997) 65. Srilalitha, S. Subha, M.C.S. and Chowdoji Rao, K., Ultrasonic studies of PEG in H2O,aqueous DMSO and DMSO solutions, J. Pure Appl. Ultrason. 18 (1996) 59. Ali, A., Nain, A. K., Sharma, V.K. and Ahmad, S.J., Acoustical studies of molecular interaction in binary liquid mixtures at 350C, Acoustical. Soc. India, 28 (2000) 283. Rajagopalan, S. and Sharma, S.J., Adiabatic compressibility and solvation studies of cellulose acetate in cyclohexane and in carbon tetrachloride, J. Pure Appl. Ultrason. 24 (2002) 1. Syal, V.K., Lal, G., Bisht, P. and Chauhan, S., Ultrasonic measurements of some 1:1 electrolytes in Chlorobenzene + Methanol mixtures, J. Mol. Liquids 63 (1995) 317. Syal, V. K., Chauhan, Anita and Chauhan, S., A study on solutions of Poly(vinylpyrrolidone) in binary mixtures of DMSO + H2O at different temperatures by ultrasonic velocity measurements, (in press, 2005). Syal, V.K., Chauhan, Anita and Chauhan, S., Ultrasonic velocity and viscosity studies on solutions of Poly (vinylalcohol) in binary mixtures of Dimethyl sulphoxide (DMSO) + H2O at 250 C, (in press, 2005). Kalyanasundaram, S., Sundaresan, B. and Hemalatha, J., Ultrasonic study on hydration of PEG using shiio model, J. Polym. Mater 19 (2001) 211. Syal, V. K., Bhalla, V. and Chauhan, S., Ultrasonic studies of some Tetraalkylammonium salts in Acetonitrile + Dioxane mixtures at 350 C, Acustica 81 (1995) 276. Syal, V. K., Kumari, Uma, Chauhan, S. and Chauhan, M.S., Ultrasonic studies of alkalibromides in Dimethylsulphoxide + Dioxane solvent mixtures at 250C, Ind. J. Pure and Appl. Phys. 30 (1992) 719. Kalyanasundaram, S., Manuel Stephan, A. and Gopalan, A..J., Ultrasonic studies of Poly (Methylacrylate) in Dimethylformamide, J. Polym. Mater. 12 (1995) 177, 323. Balokhra, R.L and Nag, A., Ultrasonic velocity of aqueous solutions of Urea, Indian J. Pure and Appl. Phys. 29 (1991) 756. Bhadha, D.R., Patel, Y.V. and Parsania, P. H.,

68

J. Pure Appl. Ultrason. Vol. 27 No. 2 & 3 (2005)

19.

20.

Ultrasonic study of Poly (R,R/,4,4/- Cyclohexylidene diphenylene phosphorochlorid-ate ) DMF solutions at different temperatures, J. Pure Appl. Ultrason. 24 (2002) 47. Singh, J., Kaur, T., Ali, V. and Gill, D.S., Ultrasonic velocities and isentropic compressibilities of some tetraalkylammonium and copper (1) salts in acetonitrile and benzonitrile, J. Chem. Soc. Faraday, Trans, 90 (1994) 579. Surendra Babu, N. and Subha, M.C.S., Effect of polymer and temperature on the critical micellar concentration of aqueous sodium dodecylsulfate, J. Indian Chem.Soc. 79 (2002) 505.

21.

22.

23.

Jones, G. and Dole, M. J., The viscosity of aqueous solutions of strong electrolytes with special reference to barium chloride, Am. Chem. Soc. 51 (1929) 2950. Syal, V.K.and Bisht, Pushpa, Viscosities of some alkali and silver metal salts in Dimethylsulphoxide + Dioxane mixtures at 35 and 450C, Proc. Indian Natn. Sci. Acad 61A (1995) 89. Sanariya, M.R. and Parsania,P.H., Studies on sound velocity and acoustical parameters of epoxy resins based on bisphenol- C, J. Pure Appl. Ultrason. 22 (2002) 54.

J. Pure Appl. Ultrason. Vol. 27 No. 2 & 3 (2005)

69