Iteratoal Joural of geerg Scece Iveto (IJSI) ISSN (Ole): 319 6734, ISSN (Prt): 319 676 www.jes.org PP. 01-06 Partal Molar olumes At Ifte Dluto For The Bary Lqud Mxtures of N-Methyl--Pyrroldoe - A Gree Solvet Wth Methyl Acetate or thyl Acetate or Butyl Acetate D. Bala Karua Kumar 1*, G. R. Satyaarayaa, R.eumadav 3 Ad Rambabu.C 4 1 Departmet of Chemstry, Adhra Loyola College, jayawada, Adhra Pradesh, Ida-50 008 Departmet of PG Chemstry, Sr C.R Reddy College, luru, Adhra Pradesh, Ida-534007 3 Departmet of Botay, SS&N College, Narasaraopet, Gutur, Adhra Pradesh, Ida 4 Departmet of Chemstry, Acharya Nagarjua Uversty, Nagarjua Nagar, Adhra Pradesh, Ida Abstract: The destes for pure lquds N-methyl--pyrroldoe (NMP a gree solvet), methyl acetate (MA), ethyl acetate (A), butyl acetate (BA) ad ther bary mxtures cotag NMP as a commo compoet have bee measured at atmospherc pressure as a fucto of composto of NMP the temperature rage 303.15-318.15 K wth a terval of 5K. From these expermetal values partal molar volumes ad excess partal molar volumes are computed. The values of excess partal molar volumes are foud to be egatve. The partal molar volumes at fte soluto are determed to hghlght the solute-solvet teractos amog the molecules the studed mxtures. The stregth of teracto of MA, A, BA wth NMP was foud to decrease wth the crease the alkyl cha legth of the ester. Key Words: Flud mxture; molecular teractos; partal molar volumes; desty; I. Itroducto The temperature varato of physcochemcal ad acoustc propertes of lqud-lqud mxtures has attracted much atteto from both the theoretcal ad egeerg applcato pots of vew. The data o some of the propertes assocated wth lquds ad lqud mxtures, lke vscosty, desty ad excess volume fd extesve applcato chemcal egeerg desg, process smulato, soluto theory ad molecular dyamcs. These propertes are mportat from practcal ad theoretcal pot of vew to uderstad lqud theory ad provde formato about molecular teractos [1-4]. N-methyl--pyrroldoe (NMP) s a watermscble orgac flud whch s hygroscopc colorless ad strogly polar. NMP s used as a solvet to mprove surface coatg ad the cleag ad degreasg of sgle-crystal slco wafers. I the plastcs dustry, t s used to dssolve may polymers. It s also used the maufacture of varous compouds, cludg cosmetcs, pgmets, sectcdes, herbcdes, pgmets, ad fugcdes. The preset work s focused to explore the solute solvet teractos by the study of partal molar volumes the bary mxtures of NMP wth some alkyl acetates (methyl acetate, ethyl acetate, butyl acetate) over the complete composto rage of NMP at temperatures of 303.15, 308.15, 313.15 ad 318.15 K ad atmospherc pressure at fte dluto. II. xpermetal Secto The pure solvets, of hghest purty commercally avalable were used the preset vestgato. NMP (Merck >99%) was dstlled at low pressure ad stored over freshly actvated 3A molecular seves. methyl acetate (MA), ethyl acetate (A) of AR grade procured from S.D fe chemcals (Ida) ad butyl acetate (BA) procured from Loba Chemcals were purfed by usg fractoatg colum [5] ad the mddle fractos were used for the expermetal study. The purty of the chemcals was assessed by comparg ther measured destes (ρ) ad ultrasoc veloctes (U) whch were good agreemet wth lterature [6-9] values as ca be see Table 1. The mxtures were prepared gravmetrcally usg a electroc balace (Shmadzu AY10) wth a ucertaty of ± 1x 10-7 kg ad were stored ar-tght glass bottles. The ucertaty mole fracto was estmated to be less tha 1x 10-4. It was esured that the compoets were adequately mxed before beg trasferred to the apparatus. The requred propertes were measured wth oe day of the mxture preparato. The destes, ρ, of pure lquds ad ther mxtures were determed usg a 10-5 m 3 double-arm pycometer as descrbed by Nkam et al [10]. The desty values from trplcate replcato at each temperature were reproducble wth ( 4 x 10 - kg m -3 ). Two-Day Iteratoal Coferece o Materals for ergy ad vrometal Protecto (ICMP-18) 1 Page
Partal Molar olumes At Ifte Dluto For The Bary Lqud Mxtures Of N-Methyl The ultrasoc velocty of pure compoets was measured by sgle crystal varable path fxed frequecy terferometer provded by Mttal terprses, New Delh (Model-F 05). The measuremets of ultrasoc velocty were take at a fxed frequecy of MHz. The calbrato of ultrasoc terferometer was doe by measurg the velocty AR grade bezee ad carbo tetrachlorde. Stadard value of U for bezee ad carbo tetrachlorde were calculated from the lterature value 38 of U at 98 K ad velocty gradet wth respect to temperature.e., the rate of chage of velocty wth temperature. Our measured values of U agree closely wth the lterature values. The measured speeds of soud were foud to be accurate up to 0.1 m s -1. Temperature cotrol for the measuremet of vscosty, desty ad ultrasoc soud speed was acheved by usg a mcroprocessor asssted crculatg water bath, (suppled by Mac, New Delh) regulated to ±0.01 K, usg a proportoal temperature cotroller. Table 1 Comparso of expermetal values of desty, ρ, ultrasoc speed, U, ad of pure lquds wth the correspodg lterature values at 303.15 K 10-3 x ρ (kg m -3 ) U (m s -1 ) Lqud xpt Lt. xpt Lt. N-methyl--pyrroldoe 1.038 1.0376 [6] 155.8 155 [7] Methyl Acetate 0.905 0.9013 [8] 113.3 1133 [8] thyl Acetate 0.8884 0.8884 [8] 1117. 1118.5 [9] 0.8889 [9] Butyl Acetate 0.8715 0.8719 [8] 1165.1 1163.6 [8] III. Theoretcal Cosderatos Assumg that ultrasoc absorpto s eglgble, usg the measured data, the thermodyamc parameters such as molar volume ( m ) ad partal, excess partal molar volumes are calculated usg stadard expressos [], The molar volumes ( m ) of the bary mxtures are calculated usg the equato x M x M 1 1 = m.. (1) where M 1, M are the molecular masses ad x 1, x are the mole fractos of lqud 1 ad lqud respectvely. The partal molar volumes of compoets 1 (NMP) ad (alkylame PA or BA or DPA), respectvely, sde the bary lqud mxtures are calculated from ther molar volumes, usg the relatos gve below [3] 0 m (1 x ) () m, 1 m 1 1 m x 1 T, P T, P 0 m x (3) m 1, x 1 0 0 where ad are the molar volumes of the pure NMP ad alkyl ame (PA or BA or DPA) respectvely. 1 Ths method leads to the partal molar volumes as coveyed by the relatoshps gve below: 0 1 x A 1 x ) x (1 x ) A (1 x ) m, 1 1 0 (.. (4) 0 1 1 x ) A (1 x ) x (1 x ) A (1 x ) m, ( (5) 0 1 The excess partal molar volumes are calculated usg the partal molar volumes wth the help of the followg equatos * m, 1 m,1 1 (6) * m, m,... (7) 1 Two-Day Iteratoal Coferece o Materals for ergy ad vrometal Protecto (ICMP-18) Page
Partal Molar olumes At Ifte Dluto For The Bary Lqud Mxtures Of N-Methyl I. Results Ad Dscusso The values of partal molar volumes ad m, 1 m, are placed Table. From Table t s evdet that for both the compoets the mxture the values of ad are smaller tha ther respectve molar m, 1 m, volumes the pure state,.e, a reducto volume s foud to occur o mxg NMP wth alkyl ames uder study. Table Partal molar volumes ( m, ) for the bary mxtures of NMP ad alkyl esters (MA or A or BA) at temperatures of 303.15, 308.15, 313.15 ad 318.15 K x 1 10 6 x /m 3 mol -1 10 6-1 x /m 3 mol m,1 303.15K 308.15K 313.15K 18.15K 303.15K 308.15K 313.15K 318.15K N-methyl--pyrroldoe(1) + methyl acetate() 0.0000 94.935 95.65 96.053 95.663 80.478 81.157 81.53 8.311 0.0845 95.95 96.044 96.051 96.100 80.445 81.144 81.531 8.9 0.170 96.018 96.104 96.199 96.481 80.435 81.136 81.508 8.36 0.66 95.916 96.148 96.438 96.83 80.463 81.13 81.440 8.141 0.3565 95.951 96.304 96.70 97.136 80.444 81.051 81.313 8.001 0.4539 96.17 96.560 97.006 97.46 80.90 80.874 81.118 81.803 0.5549 96.463 96.830 97.6 97.687 79.99 80.599 80.857 81.538 0.6598 96.681 97.08 97.466 97.90 79.659 80.97 80.544 81.05 0.7688 96.765 97.13 97.597 98.050 79.459 80.065 80.19 80.839 0.881 96.787 97.163 97.651 98.115 79.349 79.870 79.973 80.545 1.0000 96.86 97.196 97.655 98.119 78.457 79.187 79.983 80.566 N-methyl--pyrroldoe(1) + ethyl acetate() 0.0000 93.47 96.061 96.3 95.977 99.167 99.819 100.617 101.33 0.10 93.945 96.093 96.69 96.610 99.140 99.816 100.614 101.90 0.038 94.485 96.56 96.576 97.074 99.041 99.785 100.556 101.07 0.3050 95.004 96.491 96.90 97.397 98.864 99.704 100.439 101.098 0.4057 95.466 96.730 97.185 97.61 98.609 99.57 100.94 100.975 0.5060 95.860 96.95 97.36 97.787 98.79 99.409 100.147 100.837 0.6057 96.188 97.053 97.481 97.918 97.868 99.50 99.998 100.673 0.7050 96.453 97.1 97.569 98.01 97.36 99.1 99.83 100.477 0.8038 96.654 97.155 97.69 98.090 96.744 99.01 99.646 100.68 0.901 96.781 97.180 97.656 98.118 96.000 98.87 99.500 100.110 1.0000 96.86 97.196 97.655 98.119 95.19 98.495 99.583 100.148 N-methyl--pyrroldoe(1) + butyl acetate() 0.0000 96.077 96.86 96.495 96.57 133.87 134.07 134.819 135.780 0.137 96.107 96.486 96.908 97.331 133.117 133.88 134.498 135.406 0.560 96.499 96.849 97.91 97.744 13.917 133.591 134.47 135.157 0.3711 96.740 97.07 97.504 97.949 13.749 133.448 134.098 135.00 0.4785 96.816 97.157 97.589 98.04 13.544 133.64 133.867 134.758 0.579 96.819 97.171 97.616 98.08 13.79 13.978 133.554 134.411 0.6737 96.814 97.169 97.67 98.101 131.989 13.64 133.74 134.15 0.766 96.80 97.17 97.639 98.111 131.738 13.86 133.095 134.05 0.8463 96.830 97.183 97.650 98.117 131.576 13.041 13.98 133.9 0.953 96.831 97.193 97.655 98.119 131.53 131.96 13.471 133.45 1.0000 96.86 97.196 97.655 98.119 131.556 131.918 134.819 131.178 m, Table 3 xcess partal molar volumes ( x 1 m, ) for the bary mxtures of NMP ad alkyl esters (MA or A or BA) at temperatures of 303.15, 308.15, 313.15 ad 318.15 K 10 6 x /m 3 mol -1 10 6-1 x /m 3 mol m,1 303.15K 308.15K 313.15K 318.15K 303.15K 308.15K 313.15K 318.15K N-methyl--pyrroldoe(1) + methyl acetate() 0.0000-1.891-1.544-1.60 -.456 0.000 0.000 0.000 0.000 0.0845-0.901-1.15-1.604 -.019-0.033-0.013-0.001-0.019 0.170-0.808-1.09-1.456-1.638-0.043-0.01-0.04-0.075 0.66-0.910-1.048-1.17-1.96-0.015-0.034-0.09-0.170 0.3565-0.875-0.89-0.935-0.983-0.034-0.106-0.19-0.310 Two-Day Iteratoal Coferece o Materals for ergy ad vrometal Protecto (ICMP-18) m, 3 Page
Partal Molar olumes At Ifte Dluto For The Bary Lqud Mxtures Of N-Methyl 0.4539-0.654-0.636-0.649-0.693-0.188-0.83-0.414-0.508 0.5549-0.363-0.366-0.393-0.43-0.486-0.558-0.675-0.773 0.6598-0.145-0.168-0.189-0.17-0.819-0.860-0.988-1.106 0.7688-0.061-0.073-0.058-0.069-1.019-1.09-1.313-1.47 0.881-0.039-0.033-0.004-0.004-1.19-1.87-1.559-1.766 1.0000 0.000 0.000 0.000 0.000 -.01-1.971-1.549-1.745 N-methyl--pyrroldoe(1) + ethyl acetate() 0.0000-3.355-1.135-1.333 -.14 0.000 0.000 0.000 0.000 0.10 -.881-1.103-1.386-1.509-0.07-0.003-0.003-0.033 0.038 -.341-0.940-1.079-1.045-0.16-0.034-0.061-0.116 0.3050-1.8-0.705-0.735-0.7-0.303-0.115-0.178-0.5 0.4057-1.360-0.466-0.470-0.498-0.558-0.47-0.33-0.348 0.5060-0.966-0.71-0.93-0.33-0.888-0.410-0.470-0.486 0.6057-0.638-0.143-0.174-0.01-1.99-0.569-0.619-0.650 0.7050-0.373-0.074-0.086-0.098-1.805-0.697-0.785-0.846 0.8038-0.17-0.041-0.06-0.09 -.43-0.798-0.971-1.055 0.901-0.045-0.016 0.001-0.001-3.167-0.947-1.117-1.13 1.0000 0.000 0.000 0.000 0.000-4.038-1.34-1.034-1.175 N-methyl--pyrroldoe(1) + butyl acetate() 0.0000-0.749-0.910-1.160-1.547 0.000 0.000 0.000 0.000 0.137-0.719-0.710-0.747-0.788-0.014-0.01-0.033-0.051 0.560-0.37-0.347-0.364-0.375-0.109-0.109-0.14-0.147 0.3711-0.086-0.14-0.151-0.170-0.17-0.09-0.19-0.39 0.4785-0.010-0.039-0.066-0.077-0.70-0.69-0.80-0.306 0.579-0.007-0.05-0.039-0.037-0.73-0.84-0.309-0.351 0.6737-0.01-0.07-0.08-0.018-0.64-0.79-0.38-0.38 0.766-0.006-0.04-0.016-0.008-0.8-0.90-0.360-0.408 0.8463 0.004-0.013-0.005-0.00-0.31-0.336-0.406-0.431 0.953 0.005-0.003 0.000 0.000-0.3-0.413-0.44-0.447 1.0000 0.000 0.000 0.000 0.000-0.158-0.484-0.417-0.443 The values of excess partal molar volumes are provded Table 3. From table 3 t s evdet that excess partal molar volumes are egatve dcatg ter molecular teractos the bary mxtures uder study. The computed results for excess partal molar volumes (, ) of alkyl esters, Ma or A or BA ( ther bary mxtures wth NMP ( m 1 m, ) at 303.15 K are show Fg. 1. m, ) Two-Day Iteratoal Coferece o Materals for ergy ad vrometal Protecto (ICMP-18) 4 Page
1m Partal Molar olumes At Ifte Dluto For The Bary Lqud Mxtures Of N-Methyl 3.5 PARTIAL MOLAR OLUMS 0.0 1.9-0.9 0.3 m -1.8-1.3 -.9 -.7-4.5 0.0 0. 0.4 0.6 0.8 1.0 Mole fracto of NMP -3.6 From Fg. 1 t s clear that the calculated results for excess partal molar volumes ( m, ) of alkyl acetates, MA (Δ) or A ( ) or BA (o) ad ther bary mxtures wth NMP ( m, 1 ) at 303.15 K are egatve. xamato of fgure 1 dcates that cotracto partal molar volume takes place ether NMP s mxed wth the three alkyl acetates (sold le) or vce versa (dotted le) cofrmg the strog teractos betwee the ulke molecules whch support the dpole-dpole type of teracto betwee ester ad NMP as reported by us prevously []. The, values at other hgher temperatures follow the same treds but show dfferet values, m ad hece the data s ot graphcally dsplayed to mmze the umber of plots.. Coclusos Partal molar volumes ad excess partal molar volumes are computed for the bary mxtures of N- methyl--pyrroldoe (NMP) or methyl acetate (MA), ethyl acetate (A), butyl acetate (BA) the temperature rage 303.15-318.15 K wth a terval of 5K. The computed values of, are foud to be egatve for all the three bary mxtures over the etre rage of composto the temperature rage 303.15 to 318.15 K. The egatve values of partal molar volumes of the systems the preset vestgato dcate the cotracto volume of the other compoet, by the addto of NMP, suggestg the stroger termolecular teractos. A comparso of data at dfferet temperatures shows that the temperature coeffcet s decreasg for all mxtures wth creasg temperature. The teracto of NMP wth the alkyl esters uder study decreases wth the crease alkyl cha legth ad follows the order: NMP + MA > NMP +A > NMP + BA I. Ackowledgemets Oe of the authors, Bala Karua Kumar, D wshes to thak Uversty Grats Commsso of Ida for sactog MRP-4690/14. He also expresses hs gratefuless to DST Ida for gvg FIST status to Adhra Loyola College, jayawada. m Refereces [1]. Areh Be-Nam, Molecular theory of solutos, Oxford Uversty Press, (006). []. D.B.K. Kumar, K.R. Reddy, G. Srvasarao, P.B. Sadhyasr, Z. Begam, C. Rambabu, J. Mol. Lq., 183 (013) 31 44. [3]. D.B.K. Kumar, K.R. Reddy, G. Srvasarao, G.. Ramarao, C. Rambabu, J. Mol. Lq., 174 (01) 100 111. [4]. Red, R. C.; Praustz, J. M. The Propertes of Lquds ad Gases; McGraw-Hll: New York, 1986. Two-Day Iteratoal Coferece o Materals for ergy ad vrometal Protecto (ICMP-18) 5 Page
Partal Molar olumes At Ifte Dluto For The Bary Lqud Mxtures Of N-Methyl [5]. J. A. Rddck, W. B. Buger ad T. K. Sakao, Orgac Solvets. Wley-Iterscece. New York, USA, 4th edto, 1986. [6]. Y. Chagsheg, G. He, H. Yfu, P. Ma, J. Chem. g. Data 53 (008) 1639-164. [7]. P.G. Kumar, P. ekatesu, M..P. Rao, M.J. Lee, H.M. L, J. Chem. Thermody. 41 (009) 184-590 [8]. G.S. Reddy, A.S. Reddy, M.. Subbaah, A. Krshaah, J. Sol. Chem. 39 (010) 399 408 [9]. S. Asrabau, B.R. Kumar, N. Satyaarayaa, J. Chem. g. Data 55 (010) 1067 1071 [10]. P. S. Nkam,. T. R Mahalel, M. Hasa,. J. Chem. g. Data 43 (1998) 436-440. Two-Day Iteratoal Coferece o Materals for ergy ad vrometal Protecto (ICMP-18) 6 Page