International Journal of Chemical Science and Technology

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1 vlble onlne t Interntonl Journl o Checl Scence nd Technology Unverl Reerch Publcton. ll rght reerved btrct ISSN Orgnl rtcle Therodync tudy o bnry lqud xture o Wter nd DMSO t T = 08.5 K Hrh Kur * nd Deepk ** *Dept. o Chetry, Ch. Dev Ll Unverty, Sr (Hryn) Ind ** Dept. o Chetry, Snghn Unverty, Rjthn. * uthor or correpondence: hroudgl@yhoo.co.n Receved 08 Mrch 0; ccepted 7 Mrch 0 Therodync tude lke denty ( ), ultronc peed ( u ) nd exce olr volue ( V ) o bnry lqud xture o Wter + DMSO hve been crred out over the derent rnge o copoton t 08.5 K. Therodync preter lke entropc copreblty K, ntercton preter,, Flory preter, coecent, nd tndrd devton, ( Y ) hve been coputed ro experentl ndng. The exce therodync uncton hve been tted to the Redlch-Kter polynol equton. The experentl ultronc peed hve been nlyzed n ter o Jcobon Free Length Theory (FLT), Sch Collon Fctor Theory (CFT), Nooto relton, nd Vn Del del xture relton. Interoleculr Free Length, L, nd vlble volue, V, hve been clculted ro FLT, CFT nd therocoutc pproch. 0 Unverl Reerch Publcton. ll rght reerved Key Word: Ultronc Speed, xce Molr Volue, Sch Collon Fctor Theory, Wter nd DMSO. Introducton: The therodync nd coutc properte re very eentl or undertndng the phycochecl behvor o the bnry nd ult-coponent lqud xture. xce properte o lqud yte, uch olr volue, re requred or tetng the theore o oluton, developent o eprton technque nd equpent, nd or other ndutrl pplcton. DMSO n portnt polr olvent. It le toxc thn other eber o th cl uch dethylorde, dethylcetde, N-ethyl-- pyrroldone, nd hex ethyl phophorde. Becue o t excellent olvtng power, DMSO requently ued olvent or checl recton nvolvng lt. Thu, tudy o phycl properte dt on the bnry xture contnng DMSO h ttrcted conderble nteret n the lterture [- ]. Thu, Wter n DMSO xed olvent would enble u to hve lrge nuber o olvent wth pproprte phycochecl properte, whch cn be ued or prtculr checl proce. Moreover, lterture urvey ndcte tht no ultronc tudy on th bnry yte h been reported t 08.5 K. Thereore, preent tudy w undertken n order to hve deeper undertndng o the nteroleculr ntercton between the coponent o the bove bnry lqud xture. Thu, tudy o therodync properte dt on the bnry xture o H O n DMSO h ttrcted conderble nteret n our preent tudy. Reerch worker n the pt hve hown tht NMR [4, 5], IR [6-7] nd Rn pectr [8], hve been ued to tudy oleculr ntercton. The velocty eureent o the propgton o ultronc wve [9-] nd ther borpton [4, 5] hve lredy been ound to be ueul n the tudy o oleculr ntercton or norgnc, orgnc nd orgno-etllc bnry yte. Lkewe, reercher [6- ] hve lo eployed ultronc eureent to look nto the portnt conequence o on-olvent ntercton or the tructure o electrolytc oluton. Reerence [, ] relted to the eld o edcne, where reerence [4-7] bed on tude on eulon/croeulon, polyer urctnt ntercton [8] nd ultronc detructon o urctnt [9] re only ew ce to ugget vertlty o the technque. Interntonl Journl o Checl Scence nd Technology 0; (): -8

2 Tble. Dente, ultronc peed u, entropc copreblte octon 08.5K. x (DMSO) R, coutc pednce Z nd Molr ound peed (g/c ) u (/) K 0 0 ( /N) K, Interoleculr ree length Interntonl Journl o Checl Scence nd Technology 0; (): -8 L 0 L, Reltve R o bnry lqud xture o wter nd DMSO t R Z 6 0 kg Tble. Coecent o Redlch-Kter polynol equton long wth tndrd devton ( Y ) o bnry lqud xture. Properte 0 4 ( Y ) Wter + DMSO ( 0 /N) K V 0 6 / ol xperentl: DMSO w procured ro Fcher Scentc Ltd. nd w urther pured by the ethod gven n Vogel text book o prctcl orgnc chetry [0]. Pror to the experentl eureent, both the orgnc lqud were tored n drk bottle over 0.4 n oleculr eve to reduce wter content nd were prtlly deged wth vcuu pup under ntrogen tophere. The purte o ll the ple deterned by chrotogrphc nly were better thn on olr b. Bnry xture re prepred by xng pproprte volue o the lqud coponent n the peclly degned gl bottle wth r tght Telon coted cp. The therodync properte re eured on the e dy edtely ter preprng ech copoton. The uncertnty n ole rcton ± ult requency dgtl croeter redng ultronc ntereroeter (M-8, Mttl nterpre, New Delh) opertng t,, nd 4 MHz w ued to eure the ultronc velocty o the R bnry lqud xture (wth n uncertnty o ± 0.%) t contnt teperture o 08.5 K by ung dgtl contnt teperture wter bth. The teperture tblty ntned wthn ± 0.00 K by crcultng therotted wter round the cell wth crcultng pup. In order to nze the uncertnty o the eureent, everl x re llowed to p nd ther nuber (ty) counted. ll x re recorded wth the hghet wng o the needle on the croeter cle. The totl dtnce, d (c) oved by the relector gven by n, where the d wvelength. The requency,, o the crytl beng ccurtely known (.0 MHz), the peed o ound, u, n - clculted by ung the relton u. xce olr volue, V, w clculted by peclly degned double lbed gl dltoeter tted wth crocpllry (± 0.0 c) n the centre. The denty o oluton w eured by double r pyknoeter o 0 l bulb cpcty nd

3 Tble. Theoretcl vlue o ultronc peed clculted ro FLT, CFT, Nooto nd Vn Del nd Vngeel del xng relton nd percentge error n clculted vlue or Wter + DMSO. x DMSO u (/) % error FLT CFT NOM VD FLT CFT NOM VD cpllry o n nternl deter o bout.0. The rk o the te w clbrted by double dtlled wter (conductvty le thn 0-6 oh - c - ) wth nd g c - t denty t 98.5 K nd 08.5 K, repectvely nd benzene wth buoyncy corrected. The ccurcy o the denty reult w ± (g c - ). Beore ech ere o eureent, the ntruent w clbrted wth trple dtlled rehly deged wter. The ccurcy o the denty reult w ± (g/c ). Weght eureent were perored on Mettler Toledo B 5- S/FCT, ngle pn nlytcl blnce, wth precon o 0.0 g. The dente, nd ultronc velocte, u, o the pure lqud were n good greeent wth the vlue ound n the lterture nd re preented n Tble. Reult: The exce olr volue, V, o the oluton were lo clculted theoretclly ro the dente o the pure lqud nd ther xture ung the ollowng equton []: xm xm xm x M V () x Where the denty o the xture x nd x, M, nd x, M, re the ole rcton, olr, nd the denty o pure coponent nd repectvely. The ollowng relton hve been ued to correlte the ound velocty, u, o the bnry lqud xture: Nooto Relton [] R xr xr u () Vx xv xv Where x, x, V, V nd R, R re ole rcton, olr volue, nd olr ound velocty o rt nd econd coponent, repectvely. Vn Del Relton [] x x. () x M x M u M u M u d. x Where, M, M nd u, u re the olr e nd ound velocte o rt nd econd coponent, repectvely, nd ud. x the ultronc velocty o the del xture. Jcobon Free Length Theory (FLT) [4] K ux (4) L ( x.) Interntonl Journl o Checl Scence nd Technology 0; (): -8 x Where K the Jcobon contnt whch teperture dependent only nd t vlue 64.5 t.5 K. The the nteroleculr ree length o the bnry xture, L ( x.) whch gven by L V. Here V repreent the vlble Y

4 volue per ole nd Y the urce re per ole nd thee y be expreed T 0 V V V (5) Y 6 N V0 (6) Here N the vogdro nuber nd V0 nd VT re the olr volue t zero Kelvn nd t teperture T, repectvely. The V0 cn be obtned ro the ollowng relton ung crtcl teperture T C : 0. T V0 VT (7) Tc The crtcl teperture, T C the ole rcton ddtve o the vlue o t pure coponent nd gven by the relton: T x T x T (8) C C() C() The therodync nteroleculr ree length, L, n the bnry lqud xture hve been clculted ung the relton: VT xv 0() xv0() L (9) xv x V The ultronc nteroleculr ree length L, hve lo been coputed ung the Sch relton or vlble voluev : u V VT (0) u Where, u the ultronc velocty t teperture T nd u Sch Collon Fctor Theory (CFT) [5-6] x b xb ux u x x () V Where, b nd re the geoetrc volue nd collon ctor, repectvely. The ctul volue o the olecule per ole o the lqud h been coputed ung the relton 4 b r N () Where, r the oleculr rdu whch h been coputed ung the Sch relton [6] ' b r 6 N x () ' b M RT Mu u RT (4) ' Where, b the Vnder Wl contnt nd equl to our te the ctul volue o the olecule per ole o the lqud,.e. ' b 4b. (5) The therocoutcl ethod [7-9] h lo been eployed to obtn the vlble volue, V, ung the relton V V T ' V '' ' K T (6) K K ' '' The K, K, nd K re known otherl, obrc nd ochorc coutcl preter, repectvely, nd cn be expreed by the relton * ' '' S T X K K K T (7) '' X K T (8) S * T K T (9) * 4T S (0) The X known the obrc teperture coecent o nternl preure nd cn be expreed T X ~ () C V ~ Where V repreent the reduced olr volue nd C the Moelwyn-Hughe preter nd cn be expreed ~ T V () T 4T C () T The therl expnon coecent,, h been clculted ung the equton: (4) T P 4 Interntonl Journl o Checl Scence nd Technology 0; (): -8

5 The entropc copreblty hve been clculted ro Newton-Lplce equton: k (5) u The exce entropc copreblty w ound out by ung the relton, d k k k (6) Where, k d the entropc copreblty or the del xture, w obtned ccordng to Benon nd Kyohr [40] nd cree [4]: d TV (7) k k, T xv C p, xc p, Where, the volue rcton o coponent n the xture, x the correpondng ole rcton, T the bolute teperture, nd k,,v, nd C p, re the entropc copreblty, the olr volue, the cubc expnon coecent, nd the olr het cpcty o pure coponent repectvely. The cubc expnon coecent were obtned ro experentl denty eureent perored n our lbortory t derent teperture. The exce entropc copreblty o the bnry xture were tted wth Redlch-Kter polynol equton [4]: n j j (8) j0 k x x ( x x ) Where, re the djutble preter. j Owl [4] extended the Prgogne Flory-Ptteron (PFP) theory to ette the entropc copreblty nd peed o ound o lqud xture. t gven teperture, T, the PFP theory cn be ued to clculte the olr volue, V nd the olr het cpcte, C, o lqud xture the ntercton preter,, known. p Y Y X Y X Y () x Where, Y ndcte the preter uch entropc copreblty, nter oleculr ree length nd ultr onc peed: X nd X re the ole rcton o coponent nd repectvely. Y, Y, Y, nd Y x re the devton preter, preter o the coponent nd nd oberved preter repectvely. The nuber o contct te per egent o olecule, h been etted ung Bond ethod [44]. Moleculr ntercton preter or ech bnry xture w obtned by ttng the PFP theory to the correpondng H experentl equolr vlue [45-46]. Once the ntercton preter obtned, the entropc copreblty nd the peed o ound cn be etted. Dcuon : Speed o ound, u, denty, entropc copreblty, k, nteroleculr ree length, L, reltve octon, R, nd devton n peed o ound o bnry xture o H O + DMSO over the derent copoton rnge t teperture o 08.5 K re reported n Tble. The vlue o the coecent o Redlch-Kter polynol equton or ll the bnry xture long wth vlue o the tndrd devton re repreented n Tble or H O + DMSO bnry lqud xture t 08.5 K. Tble gve theoretcl vlue o ultronc peed clculted ro FLT, CFT, Nooto nd Vn Del nd Vngeel del xng relton nd percentge error n clculted vlue or DMSO + H O t 08.5 K. In pure DMSO, there dpole dpole well the uul dperve ntercton. The eect o ddng polr econd coponent prrly to drupt the dpolr ntercton o the rt coponent, but when the econd coponent polr, the dpole-dpole ntercton between unlke polr olecule ot lkely whch reult n contrcton o volue nd the xture becoe the le copreble. Inter oleculr ree length nd reltve octon h been clculted by the ollowng orul: L R K K (9) 0 0 u u (0) Where ρ 0 nd u 0 re the dente nd ultronc peed o pure olvent, ρ nd u re the denty nd ultronc peed o xture repectvely nd K the teperture dependent Jcobon contnt ( t 5 0 C). The devton preter o bnry lqud xture hve been evluted ung the generl equton: Fgure. Moleculr tructure o DMSO nd Wter. The behvor o bnry lqud xture cn be explned n ter o ) phycl orce -dperon ) checl orce dpole-dpole ntercton. The orer ctor ncree the nteroleculr ree length decrbed by Jcobon. Th turn, cue negtve devton n ound peed nd potve devton n copreblty. On the other hnd, the ltter 5 Interntonl Journl o Checl Scence nd Technology 0; (): -8

6 ctor decree the nteroleculr pth length ledng to potve devton n ound peed nd negtve devton n copreblty nd exce olr volue, V. The ctul vlue depend upon the reltve trength o two oppong eect. The concluon urther orted by the ncreng vlue o reltve octon, R ncluded n Tble. ll the trend o the bove preter ndcte tht the xture re le copreble thn ther correpondng del xture. Generlly, the devton preter condered to be the relectng gent o the gntude o polrty t the te o ntercton n the olecule. The nteroleculr ree length, L, cn be relted to the pce llng blty ung tht the olecule re ncopreble hrd phere hvng unor rdu. The nteroleculr ree length, L, or the (DMSO + H O) decree wth the ncree n ole rcton o DMSO (Tble ). The reltve octon, R, or the (DMSO + H O) ncree wth the ncree n ole rcton o DMSO (Tble ). Both thee reult prove tronger dpoledpole checl ntercton between unlke polr olecule whch reult n contrcton o volue. The tudy o tndrd devton, k, preented n Tble, revel tht the reult o ultronc velocty or DMSO wth H O yte cn be tctorly explned by Vn Del Idel Mxture relton (nu < 0.). However, the predcton o thee reult better or the DMSO wth H O yte by the CFT orulton. Theoretcl vlue o ultronc peed clculted or FLT theory how lrge percentge error n DMSO wth H O bnry lqud xture t 08.5 K (Tble ). Theoretcl vlue o ultronc peed clculted or Nooto nd Vn Del nd Vngeel del xng relton re lot dentcl. Thee relton how nu percentge error n theoretcl ultronc peed. Concluon: Denty ( ), ultronc peed ( u ) nd olr exce volue ( V ) o bnry lqud xture o H O + DMSO hve been oberved over the entre rnge o copoton nd t 08.5 K. Fro thee experentl reult, preter uch devton n entropc copreblty, K, ntercton preter,, Flory preter, Coecent, tndrd devton ( Y ) nd olr ound velocty, R, hve been etted. The exce uncton hve been tted to the Redlch-Kter polynol equton. The experentl ultronc velocte hve been nlyzed n ter o Nooto relton, Vn Del del xture relton, Jcobon Free Length theory nd Sch Collon Fctor theory. Interoleculr Free Length, L, nd vlble volue, V, hve been clculted ro Jcobon Free Length theory, Sch Collon Fctor theory, nd Therocoutc pproch or bnry lqud yte o H O + DMSO t 08.5 K. The oberved negtve vlue o K nd exce olr volue V nd potve vlue o u or thee xture ply tht the pecc checl dpole-dpole ntercton between unlke olecule donte over the phycl dperve ntercton nd dpole-dpole ntercton between lke olecule. Reerence: [] T. M. nbhv, K. Bnerjee: Denty, vcoty, rerctve ndex, nd peed o ound n bnry xture o DMSO wth ethyl cette, ethyl cette, N-propyl cette, N-butyl cette, nd -ethylbutyl--cette n the teperture ntervl ( ) K. J. Che. ng. Dt, 4 (998) [] W. Hjun, Z. Goukong, C. Mngzh: Vpor-Lqud qulbr o -Propnol or -Propnol wth,,4- Trethylpentne t 0. kp. J. Che. ng. Dt, 6 (994) [] J. S. Sndhu,. Sngh: xce olr volue o (DMSO + n n-lkn--ol) t the teperture 98.5 K. J. Che. Therodyn., 4 (99) [4] W. Ln, S. J. Ty: Nucler gnetc reonnce tude on the nteroleculr octon n oe bnry xture. J. Phy. Che., 74 (970) [5] W. G. Schneder, D. d. Hdr: Hydrogen Bondng. Pergon Pre, London, 959, 55. [6]. Grunwld nd W. C. Coburn: Group contrbuton to the therodync properte o non-onc orgnc olute n dlute queou oluton. J.. Che. Soc., 80 (958) - 5. [7] N. D. Coggehll,. L. Ser: Study o oleculr ntercton n ternry xture through ultronc peed eureent. J.. Che. Soc., 7 (95) [8] G. C. Pentel,. L. Mclelln: The Hydrogen Bond, Freen nd Co, Sn Frncco, 960, 67. [9] N. Prd, S. Prkh: Solute-wter ntercton nd the olublty behvor o long-chn prn hydrocrbon. cutc, 6 (976) -9. [0] K. Gopl, N. P. Ro: Therodync properte o queou orgnc olute n relton to ther tructure. coutc Letter, 4 (98) 64. [] F. Frnk, M.. J. Quckenden, Red, D. S., Wton, B.: derentlcloreter or the eureet o het o oluton t hgh dluton. Trn Frdy Soc., 66 (970) Interntonl Journl o Checl Scence nd Technology 0; (): -8

7 [] M. V. Kulgud, K. S. M. Ro, Ultronc velocty nd vcoty o bnry lqud xture. J. Che. Soc. Frdy Trn I, 75 (979) 7-5. [] T. N. Srvtv, R. P. Sngh, B. Swroop, Theoretcl evluton o ultronc velocty n bnry lqud xture. Ind. J. Pure ppl. Phy., (98) [4] D. Sette, Voluetrc properte o queou oluton o orgnc copound. III. lphtc econdry lcohol, cyclc lcohol, prry, econdry, nd tertry ne. Rcerc Sc., 5 (955) [5]. Dvnbkht, J. Long nd R. Zn, Interoleculr ntercton tude o bnry xture o norgnc nd orgnoetllc coplexe. J. Phy. Che., 8 (977) 60. [6] C. Shr, S. P. Gupt, Ultronc tude o oleculr ntercton o bnry xture o non nterctng orgnc olvent. coutc Letter, (986) 66. [7] K. N. Mehrotr, S. K. Updhy, coutcl tude o clcu op. coutc Letter, (987) 66. [8] K. N. Mehrotr,. S. Ghlut, M. J. Shr, Ultronc tude o oleculr ntercton n the oluton o lnthnu op. Collod Interce Sc., 0 (987) 0. [9] V. N. P. Srvtv, Therodync properte o Ne+n- H xture deduced ro ultronc velocty dt. coutc Letter, (988) [0] K. N. Mehrotr,. S. Ghlut, Stude on the cellr behvour o preodyu op. Collod nd Surce, 5 (989) 80. []. Kur, coutc tude o bnry xture o rotc ketone n benzene. Collod nd Surce, 4 (989) -9. [] R. Scheruly, T. Scheehl,. Gunther, F. Grnger, W. Seeger, D. Wlrth, Oxdtve Stre n Chronc Obtructve Pulonry Dee.. J. Repr. Crt. Cre. Med., 56 () (997) 445. [] M. H. Wnger, S. W. Fredrch, I. Mollenhuer, M. Obden, U. Boenck, Bo. Phy. Che., 84 () (000) 5. [4] S. Hckey, M. J. Lwrence, S.. Hgn, V. Buckn, nly o the phe dgr nd crotructurl trnton n phopholpd croeulon yte ung hghreoluton ultronc pectrocopy. Lngur, () (006) [5] L. Becu, S. Mnnevlle,. Coln, Study o trglycerdeproten ntercton ung croeulon- ltrton ethod. Phy. Rev. Lett., 76 () (006) 8. [6] Meht, S. K. Kwljet, Interoleculr ntercton tudy o croeulon nd eulon n DDB/W/ol yte. Phy. Rev.. Stt. Nonln. Sot Mtter Phy., (00) 65. [7] M. Brllev nd F. Greex, ulon Polyerzton Synthe o Ctonc Polyer Ltex n n Ultronc Feld. J. Collod Interce Sc., 5 () (00) 78. [8] D. lendr, prno Cllo L Me, L. Pert, Ultronc Nebulzton or cent Delvery o Surctnt n Model o cute Lung Injury. Ipct on G xchnge.. J. Repr. Crt. Cre Med., 56 (997) 445. [9] L. K. Wever, F. P. J. Gyng,. Y. Le, Rthn, F. Je, Benzene nvronent Reerch, 77 () (005) [0] B. S. Furn,. J. Hnnord, P. W. G. Sth,. R. Ttchell, Textbook o Prctcl Orgnc Chetry, 004, 98. [] S. C. Bht, R. Bht, G. P. Dubey, Stude on trnport nd therodync properte o bnry xture o octn--ol wth chloroor,,-dchloroethne nd,,,- tetrchloroethne t 98.5 nd 08.5 K. J. Mol. Lqud, 44() (009) 6-7. [] O. Nooto, prcl orul or ound velocty n lqud xture. J. Phy. Soc. Jpn., (958) 58. [] W. Vn Del, Therodync Properte nd Velocty o Sound, Butterworth, London, 975, Chp. 5. [4] B. Jcobon, Theoretcl tudy o ultronc velocty n bnry lqud xture t 0 0 C. ct Che. Scnd., 6 (95) [5] W. Sch, Study o oleculr ntercton n ternry xture through ultronc peed eureent. coutc, (975) [6] W. Sch, Molekulrkutc. Sprnger Verlg, Berln, 96, Chp. -. [7] R. Nutch-Kuhnke, Stude on thero-coutc preter n bnry lqud xture o phophnc cd wth derent dluent t 0.5 K. coutc, 5 (965) [8] J. D. Pndey, R. Dev, J. Chhbr, Therocoutcl pproch to the nteroleculr ree-length o lqud xture. Phy. Che. Coun. 6 (00) 55. [9] J. D. Pndey, G. P. Dubey, B. P. Shukl, S. N. Dubey, Predcton o ultronc velocty nd nteroleculr reelength nd ther correlton wth ntercton n bnry lqud xture. Prn J. Phy., 7 (6) (99) [40] G. C. Benon, O. K. Kyohr, vluton o exce entropc copreblty nd ochorc het cpcte. J. Che. Therodyn. (979) 06. [4] W.. cree, Denty, Speed o Sound, nd Ientropc Copreblty o Trethnolne (or N-Methyldethnolne) + Wter + thnol Soluton ro t = (5 to 50) C. J. Che. ng. Dt, 8 (98) Interntonl Journl o Checl Scence nd Technology 0; (): -8

8 [4] O. Redlch,. T. Kter, Repreentton o Therodync Properte nd the Clcton o Soluton. Indut. ng. Che., 40 (948) [4] S. L. Owl, R. P. Phlk, Speed o ound nd entropc copreblte o nonelectrolyte lqud xture. I. Bnry xture contnng p-doxne. J. Sol. Che. (99) [44]. Bond, Phycl Properte o Molecule, Lqud nd Ge, Wley, New York, 968. [45] K. W. Morco, xce enthlpy;,-doxne + cyclohexne nd,4- doxne + cyclohexne. Int. Dt Ser., Sec. (97) 56. [46]. Inglee, H. V. Kehn, Molr exce volue nd exce het cpcte o (,,4-trchlorobenzene + n lkne). Int. Dt Ser. Sec. (98). Source o upport: Nl; Conlct o nteret: None declred 8 Interntonl Journl o Checl Scence nd Technology 0; (): -8