Thermodynamic study of binary mixtures of methyl acrylate and ethyl acrylate with octane-1-ol

Available online at wwwpelagiaresearchlibrarycom Advances in Applied Science Research, 213, 4(3):329-337 ISSN: 976-861 CODN (USA): AASRFC Thermodynamic study of binary mixtures of methyl acrylate and ethyl acrylate with octane-1-ol Sujata S Patil a * and Sunil R Mirgane b a Dept of Applied Science, Matsyodari Shikshan Sanstha s, College of ngineering and Technology, Jalna (M S), India b P G Dept of Chemistry, J S College, Jalna (M S), India ABSTRACT Thermodynamic properties involving density and ultrasonic velocities of binary liquid mixtures of methyl acrylate and ethyl acrylate with octane-1-ol measured at 29815 and 3815 K temperatures and at atmospheric pressure These fundamental properties have been fitted to recently proposed Jouyban-Acree model xcess molar volume and deviations in isentropic compressibility were calculated from density and ultrasonic velocity respectively, and have been fitted to Redlich-Kister polynomial equation The experimental values of ultrasonic velocity were used to calculate different derived thermodynamic parameters like excess specific acoustic impendence, excess intermolecular free length, excess available volume and excess intrinsic pressure Graphical representations of all excess thermodynamic parameters used to explain type and extent of intermolecular interactions Graphical variation for all these parameters shows positive deviation for excess molar volume, deviation in isentropic compressibility, excess intermolecular free length, excess available volume and negative deviation for excess specific acoustic impendence, excess intrinsic pressure Keywords: Redlich-Kister quation, Molecular Interactions, Jouyban-Acree Model, xcess Specific Acoustic Impendence, xcess Intrinsic Pressure INTRODUCTION The knowledge of thermodynamic and physical properties of liquid-liquid systems is of considerable importance due to their wide range of applicability as solvent media in various physicochemical studies, in processing and product formation in many industrial applications Measurements of some of the bulk properties like density, viscosity and ultrasonic velocity of liquids provide an insight into the investigation of the intermolecular arrangement of liquids and help to understand the thermodynamic and acoustic properties of the liquid mixtures Volume properties and evaluation of thermodynamic properties gives the better knowledge of the processes that occur in the mixture Better understanding of these kinds of properties of fluids is essential in designing processes involving heat transfer, mass transfer and fluid flow The more information of magnitudes such as excess molar volume of a given component of a mixture, the more efficient the design of engineering processes in which these magnitudes are involved Binary liquid mixtures rather than single component liquid system are widely used in processing and product formulations in many industrial applications Among the various properties considered in process and product design and optimization excess molar volumes is most important Ultrasonic velocity measurement of liquid mixtures of non electrolytes provides an excellent tool to investigate inter and intramolecular 329

interactions between unlike and like molecules Alcohols exist in form of aggregates When they are mixed with non electrolyte molecules, aggregates of alcohol dissociate and form intermolecular complexes with unlike molecules Literature survey reveals that, molecular interactions of present binary liquid mixtures containing methyl acrylate and ethyl acrylate with octane-1-ol at temperatures 29815 and 3815 K have not much studied Attempts have been made to probe liquid structure through evaluation of density and ultrasonic velocity We have thus undertaken thermodynamic study of binary liquid systems containing many polar and non-polar liquids to investigate molecular interactions TRIALS AND MTHODS Methyl acrylate (), ethyl acrylate (A) and octane-1-ol used of mass fraction purities > 998 (-Merck) were double distilled; middle fraction collected of all liquids was stored over 4 nm molecular sieves Masses were recorded on a Mettlar balance, with an accuracy of ± 1 mg The temperature was controlled using a constant temperature controlled water bath (Gemini Scientific Instruments, Chennai, India) having accuracy ± 2 C xperimental Part Densities were measured [1] using a single capillary pycnometer made up of borosil glass with a bulb of 8 cm 3 and capillary with internal diameter of 1 cm The accuracy in density measurement was ± 5 1-5 g/cm 3 Ultrasonic velocities were measured [2] at frequency of 2 MHz by single crystal ultrasonic interferometer (Model F-81, Mittal nterprises, New Delhi, India) Accuracy in velocity measurements is ± 1 % A comparison of measured values of pure components with the literature values as presented in Table 1 shows a good agreement Table 1 Densities (ρ) and ultrasonic velocities (u) for pure components at T = 29815 and 3815 K Property T = 29815 K T = 3815 K xpt Lit xpt Lit Octane-1-ol ρ (gcm -3 ) 8216 8215 [3] 81453 81467 [4] u (ms -1 ) 1351 1347 [3] 1319 1314 [5] Methyl Acrylate ρ (gcm -3 ) 94751 9475 [6] 93561 9356 [6] u (ms -1 ) 1185 --- 114 --- thyl Acrylate ρ (gcm -3 ) 91632 9163 [6] 94 946 [6] u (ms -1 ) 1167 --- 1137 --- Computational Part xcess molar volumes of solutions were calculated from densities of pure liquids and their mixtures according to equation, V = [x 1 M 1 +x 2 M 2 ]/ρ 12 [ (x 1 M 1 /ρ 1 )+( x 2 M 2 /ρ 2 )] (1) where ρ 12 is density of mixture and x 1, M 1, ρ 1 and x 2, M 2, ρ 2 are mole fractions, molecular weights and densities of pure components 1 and 2, respectively Deviation in isentropic compressibility were calculated using, κ s = κ s - κ s id (2) where κ s is isentropic compressibility and was calculated using Laplace relation, κ s = (1/ u 2 ρ) (3) κ s id was calculated from relation, κ s id = φi[κ s,i +TV o i(α o i 2 )/C p,i ] - [T( x i V o i) ( φ i α o i) 2 / x i C p,i ] (4) 33

where φ i is ideal state volume fraction of component i in mixture stated and is defined by, φ i = x i V o i / ( x i V o i) (5) T is temperature and κ s,i, V o i, α o i, and C p,i are isentropic compressibility, molar volume, coefficient of isobaric thermal expansion and molar heat capacity respectively for pure component i α o i is calculated from measured densities by relation, α = [(ρ 1 / ρ 2 )-1]/ (T 2 -T 1 ) (6) Densities, ultrasonic velocities, excess molar volumes and deviation in isentropic compressibilities of binary liquid mixtures are summarized in Table 2 Table 2 Densities (ρ), ultrasonic velocities (u), excess molar volumes (V ) and deviation in isentropic compressibilities ( κ s) of Acrylates (1) + Octane-1-ol (2) at T = 29815 and 3815 K T = 29815 K T = 3815 K ρ V u κ s Ρ V u κ s (gcm -3 ) (cm 3 mol -1 ) (ms -1 ) (TPa -1 ) (gcm -3 ) (cm 3 mol -1 ) (ms -1 ) (TPa -1 ) (1) + Octane-1-ol (2) 8216 1351 81453 1319 552 82482 162 1341 459 81785 118 138 521 997 82782 237 1333 793 8276 191 13 827 1553 8317 339 1324 196 8246 275 1289 133 1997 83499 415 1316 145 82785 337 1281 1577 2554 83941 484 137 1662 83218 395 1271 1894 2991 8431 532 1299 1941 83579 436 1263 2137 355 84815 579 129 2134 8472 475 1252 256 3999 85248 65 1282 2347 84493 497 1244 2675 4554 85821 625 1273 2472 8549 515 1234 2853 4998 86313 625 1265 263 85524 515 1226 2961 5555 86971 618 1256 2664 86159 51 1216 341 5999 87334 61 1249 263 8672 494 128 363 6554 88292 563 124 2556 87429 464 1199 2894 6999 88946 522 1233 2419 8854 431 1191 284 7556 89825 458 1224 227 88894 378 1181 2614 7998 9582 395 1217 1954 89614 327 1174 2259 8554 9168 33 128 1576 9589 251 1164 1882 8999 92499 218 121 1169 91433 181 1157 135 9555 93717 88 1192 576 92582 75 1147 732 1 94751 1185 93561 114 A (1) + Octane-1-ol (2) 8216 1351 81453 1319 555 82479 94 134 314 8177 63 138 327 999 8275 154 1331 574 8229 118 13 497 1555 8314 223 1321 756 8237 176 1289 84 1998 83398 272 1312 1 82654 214 128 166 2556 83788 321 131 1254 8328 255 127 1225 2997 84111 354 1293 1364 83337 282 1262 1345 3551 84534 387 1283 148 83743 36 1251 1593 3999 84895 44 1274 1655 8486 322 1243 1667 4551 8536 416 1264 1727 84528 332 1233 1752 4998 85754 42 1256 1752 849 338 1225 1789 5555 86272 413 1245 1872 85392 331 1215 18 5998 8674 41 1237 1855 85799 322 127 1794 655 87268 378 1227 185 86332 3 1197 1755 6999 87752 35 1219 1713 86787 278 1189 1671 7555 88383 36 121 1442 87378 244 1179 154 7998 88912 264 122 1294 87872 21 1171 145 8554 89611 23 1192 154 88525 16 1162 135 8999 921 147 1184 817 8975 114 1154 87 955 998 56 1175 34 8982 35 1145 327 1 91632 1167 94 1137 331

From ultrasonic velocity different thermodynamic parameters like specific acoustic impendence (Z), intermolecular free length (L f ), available volume (V a ) and intrinsic pressure (π i ) can be calculated, which provides better insight in understanding of molecular interactions in pure and binary liquids, which are given by relations, Z = uρ (7) L f = K(κ s ) 1/2 (8) V a = V m [1-(u expt /u )] (9) Where M is average molecular weight, K is temperature dependent constant whose value is 19761-6 281-6 at 29815 and 3815 K respectively, u = 16 m/s and For binary liquid mixtures intrinsic pressure can be given as, π i = brt (Kη 12 /u 12 ) 1/2 (ρ 12 2/3 /M 12 7/6 ) (1) Where b is packing factor, K is a constant temperature independent having value of 428 1 9, R is gas constant and η 12, u 12, ρ 12 are mixture s viscosity, ultrasonic velocity and density The excess functions are important to understand molecular interactions between components of liquid mixtures xcess function Y represents excess of a given quantity Y of a real mixture over its value for an ideal mixture Y id at the same conditions of temperature, pressure and composition It is expressed by following relation, Y = Y - Y id (11) where Y denotes Z, L f, Va, π i and Y represents corresponding excess thermodynamic properties such as excess specific acoustic impedance (Z ), excess intermolecular free length (L f ), excess available volume (V a ) and excess intrinsic pressure (π i ) These excess thermodynamic parameters are represented in Table 3 Deviation in isentropic compressibility were fitted to Redlich-Kister [7] equation of type, n Y = x 1 x 2 i a ( x1 x2 ) (12) i i Where Y is V or κ s and n is degree of polynomial Coefficient a i was obtained by fitting q (12) to experimental results using a least-squares regression method Optimum number of coefficients is ascertained from an examination of variation in standard deviation (σ) calculated using relation, σ (Y) = ( Y 2 exp t Ycalc ) N n 1/ 2 (13) Where N is number of data points and n is number of coefficients Calculated values of coefficients a i along with standard deviations are given in Table 4 332

Table 3 xcess specific acoustic impendence (Z ), excess intermolecular free length (L f ), excess available volume (Va ) and excess intrinsic pressure (π int ) for Acrylates (1) + Octane-1-ol (2) at T = 29815 and 3815 K T = 29815 K T = 3815 K Z L f Va π int Z L f Va π int (Kgm -2 s -1 ) (m) (m 3 mol -1 ) (atm) (Kgm -2 s -1 ) (m) (m 3 mol -1 ) (atm) (1) + Octane-1-ol (2) 552-461 1 473-2772 -419 1 527-23553 997-778 2 87-33478 -66 2 828-2872 1553-18 2 192-45674 -125 2 1255-37868 1997-137 3 136-48725 -1234 3 1484-426 2554-1615 4 1565-57574 -1468 3 1729-47585 2991-1863 4 1775-58336 -1644 4 1899-4838 355-242 5 1893-6446 -193 5 2135-53196 3999-2223 5 22-63361 -217 5 2216-52147 4554-2332 5 259-66274 -2132 5 228-54886 4998-2453 6 2122-63239 -2196 5 2297-5231 5555-2475 6 276-6399 -2236 6 2269-53319 5999-2437 6 1994-59333 -2234 6 2213-49249 6554-2356 5 1869-57776 -21 5 225-48467 6999-2225 5 172-51741 -22 5 1895-4329 7556-221 5 151-4815 -1866 5 1689-4723 7998-1785 4 1298-4436 -168 4 1423-34244 8554-1432 3 15-3499 -1326 3 1127-3151 8999-16 2 724-2672 -949 2 79-22792 9555-512 1 343-18946 -53 1 41-1696 1 A (1) + Octane-1-ol (2) 555-251 389-22911 -223 393-1997 999-452 1 691-29492 -334 1 64-24228 1555-586 1 914-4618 -538 1 93-333 1998-768 1 1163-44548 -71 1 1184-35899 2556-952 2 149-52173 -82 2 1345-4248 2997-125 2 1512-542 -871 2 1455-43587 3551-198 2 168-58798 -122 2 1647-47429 3999-1217 2 1737-58557 -157 2 1694-4723 4551-1254 2 1769-6426 -197 2 1735-4962 4998-126 2 1761-58488 -119 2 1734-47362 5555-1332 3 18-57959 -111 2 1699-47297 5998-138 3 1743-54212 -187 2 1651-4452 655-1259 3 1643-51668 -15 2 1562-42257 6999-1184 3 1522-46586 -991 2 145-3816 7555-985 2 1271-425 -93 2 1288-3451 7998-876 2 119-35455 -818 2 1135-2993 8554-76 2 868-29185 -591 1 831-24335 8999-543 1 648-21394 -458 1 622-1798 955-216 278-13431 -171 264-11846 1 Table 4 Adjustable parameters of q (12) and (13) for excess molar volume (V ) and deviation in isentropic compressibility ( κ s) for Acrylates (1) + Octane-1-ol (2) at T = 29815 and 3815 K Property T (K) a a 1 a 2 a 3 a 4 σ (1) + Octane-1-ol (2) V (cm 3 mol -1 ) 29815 2512 1624-28 -7417 1396 922 3815 2596 84 194-367 -1856 475 κ s (TPa -1 ) 29815 5786 23385-81963 -97369 182221 22979 3815 563974 198298-158468 4727 349854 38183 A (1) + Octane-1-ol (2) V (cm 3 mol -1 ) 29815 16647 812 2133-3439 -4121 522 3815 13155 687 4354-2615 -9328 678 κ s (TPa -1 ) 29815 223283 12633 48396-116714 -8428 42764 3815 16816 1173 171934-116787 -27123 414 Jouyban-Acree [8-9] recently proposed model for correlating density of liquid mixtures at various temperatures The proposed equation is, 333

lny mt = f 1 lny 1T +f 2 lny 2T + f 1 f 2 [A j (f 1 -f 2 ) j /T] (14) where y mt, y 1T and y 2T is density of mixture and solvents 1 and 2 at temperature T, respectively, f 1 and f 2 are volume fractions of solvents in case of density and Aj are the model constants The correlating ability of the Jouyban-Acree model was tested by calculating the average percentage deviation (APD) between the experimental and calculated density as, APD = (1/N) [( y expt - y cal )/ y expt )] (15) where N is the number of data points in each set The optimum numbers of constants Aj, in each case, are determined from the examination of the average percentage deviation value Jouyban Acree model was not previously applied to ultrasonic velocity measurements, we extend Jouyban Acree model to ultrasonic velocity qn (14) of liquid mixtures with f as mole fraction and apply qn (15) for correlating ability of model The constants (Aj) calculated from least square analysis along with average percentage deviation (APD) are presented in Table 5 Table 5 Parameters of q (14) and (15) for Acrylates (1) + Octane-1-ol (2) Property a a 1 a 2 a 3 a 4 σ APD (1) + Octane-1-ol (2) ρ (gcm -3) -253934-65289 -23 9314 7739 58324 277 u (ms -1 ) -61-1279 1583 576-19151 1284161 187 A (1) + Octane-1-ol (2) ρ (gcm -3) -131672-23792 -12754 758 196 34139 256 u (ms -1 ) 34-1261 -1136 256 21942 1276732 211 RSULTS AND DISCUSSION V (cm 3 mol -1 ) 8 6 4 2 Fig 1 A 2 4 X 6 8 1 12 1 Fig 1 Variation of excess molar volumes for acrylates (1) + octane-1-ol (2) at 29815 K xcess molar volumes found to be positive for all the systems, where dispersion, induction and dipolar forces are operating, whereas existence of specific interactions between the mixing components of the various binary systems tends to make excess molar volumes negative [1] Since, normally dispersive interaction between unlike molecules is weaker than those between like molecules, it is reasonable that they contribute positively [11-12] to excess molar volumes Changes in excess molar volume takes place during mixing which is the result of several effects that operate in the same or opposite directions The most important ones are:- 1 A positive effect caused by the break-up of the structure of one or both components originating from nonchemical or chemical interactions, such as, hydrogen bonding or complex formatting interactions; such as, self-association 2 A negative one, due to physical interactions (heteroassociation) or geometric fitting of on component into the second, leading to a more compact packing (interstitial accommodation) The second contribution becomes more important with increasing sphericicity of the solute molecule and higher molar volume of the solvent [13] 334

3 25 Fig 2 A κ s (TPa -1 ) 2 15 1 5 2 4 6 8 1 12 Fig 2 Variation of deviation in isentropic compressibility for acrylates (1) + octane-1-ol (2) at 29815 K A strong molecular interaction through charge transfer, dipole-induced dipole, dipole-dipole [14] interactions, interstitial accommodation and orientational ordering lead to a more compact structure, making κ s negative and breakup of alkanols structures tend to make κ s positive Sign of κ s and V decides compactness due to molecular rearrangement Magnitude of various contributions depends mainly on relative molecular size of components Declustering of octane-1-ol in presence of acrylates lead to positive κ s values 2 4 6 8 1 12 Z (Kgm -2 s -1 ) -1-2 -3 Fig 3 A Fig 3 Variation of excess specific acoustic impedance for acrylates (1) + octane-1-ol (2) at 29815 K The positive values indicate the presence of strong specific interactions and negative values corresponds mainly to the existence of dispersive forces Thus from above discussion reinforces our views that in the present systems dispersion forces are dominant and the geometrical fitting is also observed L f (m) 7 6 5 4 3 2 1 Fig 4 A 2 4 6 8 1 12 Fig 4 Variation of excess intermolecular free length for acrylates (1) + octane-1-ol (2) at 29815 K 335

xcess intermolecular free lengths are found to be positive for both systems The trends are symmetric L f values increase with increase of chain length acrylates This may be due to fewer protons donating ability of 1-octanol In pure alkanols, molecules are self associated through hydrogen bond, mixing of acrylates with 1-octanol will induce rupture of hydrogen bonds in liquids with subsequent increase in L f values Deviation in compressibility and excess free length become increasingly negative with increasing strength of interaction between component molecules V a (m 3 mol -1 ) 25 2 15 1 5 Fig 5 A 2 4 6 8 1 12 Fig 5 Variation of excess available volume for acrylates (1) + octane-1-ol (2) at 29815 K Positive values of Va indicate presence of strong specific interaction This nature may be attributed to strong interactions between acrylate and alkanols On the other hand, negative values of it means weak interactions due to, possible accommodation, large difference in molar volume, dipole-dipole interactions, dipole-induced dipole interactions and van der Waal s forces of attraction π int (atm) -2-4 -6 2 4 6 8 1 12-8 Fig 6 A Fig 6 Variation of excess intrinsic pressure for acrylates (1) + octane-1-ol (2) at 29815 K xcess internal pressure π i has been used [15-2] to study the intermolecular interactions in binary liquid mixtures The values of π i are found to be negative throughout the mole fraction in all binary mixtures of alkanols with acrylate suggesting weak interactions valuated values of excess thermodynamic parameters such as excess molar volume (V ) and deviation isentropic compressibility ( κ s ) were fitted to Redlich-Kister polynomial equation at both temperatures and are represented as in Table 4 with their standard percentage deviation Redlich-Kister equation was originally developed to correlate the excess Gibb s energy function and calculate the values of the activity coefficients It turned out to be such a powerful and versatile correlating tool that its use has been extended to other properties, particularly excess molar volumes and excess enthalpies of mixing It suffers from important drawback that values of adjustable parameters change as number in series is increased, so that no physical interpretation can be attached to them [21-22] 336

The constants (Aj) calculated from least square analysis along with average percentage deviation (APD) are presented in Table 5 xperimentally measured fundamental thermodynamic properties such as density and ultrasonic velocity were correlated using recently proposed Jouyban-Acree model CONCLUSION Positive values of excess molar volumes shows volume expansion is taking place causing rupture of H-bonds in self associated alcohols Positive values of κ s observed when H-bonded aggregates of alkanols break up progressively with addition of acrylates For mixture containing alkanols, the negative values of Z suggests that, dispersive forces are dominant over the specific interaction Rupturing of hydrogen bonding in liquids leads to increase in L f values Positive values of Va indicate presence of strong specific interaction The values of π i are found to be negative suggesting weak interactions Redlich-Kister regressor is very powerful and frequently used to correlate vapourliquid equilibrium data and excess properties The proposed model provides reasonably accurate calculations for these fundamental thermodynamic parameters of binary liquid mixtures Acknowledgements Author (SSP) acknowledge Department of Science and Technology, New Delhi, Government of India, for financial support by awarding Junior Research Fellowship Authors are thankful to Prof B R Arbad, Dr B A M University for their valuable suggestions RFRNCS [1] S S Patil, S R Mirgane, Int J of Che, Pharma and nvi Res, 211, 2, 72 [2] S S Patil, S R Mirgane, J Saudi Chem Soc, 212 (In Press, Available Online) [3] Mascato, M M Pineiro, L Mosteiro, T P Iglesias, J L Legido, J Chem ng Data, 2, 45, 1154 [4] M Dzida, J Chem ng Data, 27, 52, 521 [5] D F Shirude, Ph D Thesis, Pune University (Pune, India, Feb 26) [6] N V Sastry, M K Valand, Int J of Thermophysics, 1997, 18 [7] O Redlich, A T Kister, Ind ng Chem, 1948 [8] A Jouyban, M Khoubnasabjafari, Z Vaez-Gharamaleki, Z Fekari, J W Acree, J Chem Pharm Bull, 25, 53, 519 [9] A Jouyban, A Fathi Azarbayjani, M Khoubnasabjafari, J W Acree, Ind J Chem, 25, 44, 1553 [1] T M Aminabhavi, V B Patil, J Chem ng Data, 22, 43, 54 [11] Alvarez, A Cancela, R Maceiras, J M Navaza, R Taboas, J Chem ng Data, 26, 51, 94 [12] T M Aminabhavi, K Banerjee, J Chem ng Data, 1998, 43, 59 [13] R D Peralta, R Infante, G Cortez, O Rodriguez, J Wisniak, J Sol Chem, 22, 31 (3), 175 [14] R D Rai, R K Shukla, A K Shukla, J D Pandey, J Chem Thermodyn, 1989, 21, 125 [15] J D Pandey, G P Dubey, B P Shukla, S N Dubey, J Pure App Ultrason, 1991, 13, 74 [16] J D Pandey, R L Mishra, Acustica, 1978, 39, 2 [17] M R J Dack, Aust J Chem, 1975, 28, 1643 [18] M R J Dack, J Chem Soc Rev (GB), 1975, 4, 211 [19] L I Acevedo, G Pedrosa, M Katz, J Sol Chem, 199, 19, 11 [2] R D Roy, R K Shukla, A K Shukla, J D Pandey, J Chem Thermodyn, 1989, 21, 125 [21] R D Peralta, R Infante, G Cortez, O Rodriguez, J Wisniak, J Sol Chem, 22, 31 (3), 175 [22] R D Peralta, R Infante, G Cortez, J Wisniak, J Sol Chem, 25, 34 (5), 515 [23] Thakur Saneel K, Chauhan Shivani, Advances in Applied Science Research, 211, 2(2), 28-217 [24] Bhandakkar V D, Bedare G R, Muley V D, Suryawanshi B M, Advances in Applied Science Research, 211, 2(4), 338-347 [25] Chimankar Omprakashp, Shriwas Ranjeeta, Tabhane Vilas A, Advances in Applied Science Research, 21, 1 (3), 78-85 [26] Kulshrestha Anchal, Baluja Shipra, Advances in Applied Science Research, 21, 1(3), 229-239 [27] Chimankar O P, Shriwas Ranjeeta S, Jajodia Sangeeta, Tabhane V A, Advances in Applied Science Research, 211, 2(3), 5-58 337