International Journal of Latest Research in Science and Technology ISSN (Online):2278-5299 Volume 2,Issue 1 :Page No.460-464 ,January-February(2013) http://www.mnkjournals.com/ijlrst.htm ISSN:2278-5299460 SPEED OF SOUND AND ADIABATIC COMPRESSIBILITY OF BINARY LIQUID SYSTEMS AT VARIOUS TEMPERATURES R.K.Shukla*1, G.K.Gupta2 and S.K.Pramanik2 1Department of Chemistry, V.S.S.D.College, Kanpur-208002- India. 2 Research Scholar,Department of Chemistry, Singhania UniversityJhunjhunu Rajasthan-India Abstract - Densities and speed of sound were measured for the formamide + acetonitrile binary liquid mixtures at 293.15, 298.15, 303.15, 308.15and313.15Kandatmosphericpressureovertheentireconcentrationrange.VariousliquidstatemodelslikePrigogine-Flory-Pattersonmodel(PFP),RamaswamyandAnbananthan(RS)modelandmodelsuggestedbyGlinski,wereusedtopredictthespeedof soundandadiabaticcompressibilityofweaklyinteractingliquids.ThemeasuredpropertieswerefittedtoRedlich-Kisterpolynomial relationtoestimatethebinarycoefficientsandstandarderrors.Anattempthasalsobeenmadetostudythemolecularinteractions involved in the liquid mixture from observed data. McAllister multi body interaction model was also used to correlate the binary properties. Comparativemeritsofthesenon-associatedandassociatedmodelsweretestedforformamide+acetonitrilebinaryliquidmixtures showing that the associated processes yield fair agreement between theory and experiment as compared to non-associated processes. Keywords -Ultrasonic Velocity, Prigogine-Flory-Patterson, McAllister, Ramaswamy and Anbananthan, Isentropic Compressibility and Redlich-Kister 1.IntroductionPhysicochemicalbehaviorandmolecularinteractions occurring in a variety of liquid mixtures and solutions can be studiedwiththehelpofultrasonicvelocity[1].Datawere analyzedintermsofRamaswamyandAnbananthan(RS) model[2]modelsuggestedbyGlinski[3],Prigogine-Flory-Patterson (PFP) model [4-6], First two models, RS and model devisedbyGlinski(associated)arebasedontheassociation constant as an adjustable parameters where as PFP and others (non-associated)arebasedtheadditivityofliquids.Forthat purposes, we selected the liquids containing poor associating properties.Fromtheseresults,deviationsinultrasonic velocity,!uwerecalculatedandfittedtotheRedlich-Kister polynomial equation [7] to derive the binary coefficients and thestandarderrors.Anattempthasalsobeenmadeto correlatetheexperimentaldatawiththeMcAllistermulti bodyinteractionmodel[8].Themixingbehaviorofsuch liquidmixtures is interesting due to presence of cyanogroup coupledwithamidelinkageresultinginteractionsinliquid mixtures.Theassociationalbehaviorofliquidsandtheir correlationwithmolecularinteractionshasalsobeenmade using different liquid state models. This is our first attempt to correlateallthemodels(associatedandnon-associated) simultaneouslyinpredictingtheassociationalbehaviorof binary liquid mixtures from sound velocity data. Extensive work has been carried out by many workers [9-13] toinvestigateliquidstatethroughanalysisofultrasonic propagation parameters 2. Experimental Section 2.1Materials ARgradesamplesofhighpurityusedinthis experimentwereobtainedfromMerckCo.Inc.,Germany andpurifiedbysimpledistillationandthemiddlefraction wascollected.Theliquidswerestoredindarkbottlesover 0.4nmmolecularsievestoreducewatercontentandwere partiallydegassed with avacuumpump.The purityofeach compoundwascheckedbygaschromatographyandthe resultsindicatedthatthemolefractionpuritywashigher than0.98.Thepurityofchemicalsusedwasconfirmedby comparingthedensitiesandspeedofsoundwiththose reported in the literature as shown in Table 1. 2.2Apparatus and Procedure wecalibratedtheinstrumentbeforeeachseriesof experimentsatatmosphericpressurewithdoublydistilled water.Theuncertaintyinthedensitymeasurementwas within6.4kg.m-3.Thedensitiesweremeasuredwiththe bi-capillarypyknometer.Theliquidmixtures wereprepared bymassinanairtightstoppedbottleusinganelectronic balance model SHIMADZUAX-200 accurate to within 0.1 mg.Theaverageuncertaintyinthecompositionofthe mixtures was estimated to be less than 0.0001. Crystalcontrolledvariablepathultrasonicinterferometer suppliedbyM/sMittalenterprises(model-05F),NewDelhi (India),operatingatafrequencyof2MHzwasusedinthe ultrasonicmeasurementswithanaccuracybetterthan3%. id15955407 pdfMachine by Broadgun Software- a great PDF writer!- a great PDF creator! - http://www.pdfmachine.comhttp://www.broadgun.com R.K.Shukla, International Journal of Latest Research in Science and Technology. ISSN: 2278-5299 461 Isentropiccompressibility,s,werecalculatedfromthe relation, 1 2 " "# ! " us(1) whereisthedensityanduistheultrasonicvelocity.The estimatederrorinthecalculationofisentropic compressibility was found to be 2.5 T Pa!1. TheresultsarelistedinTable1togetherwithliterature values [14] for comparison and3. Modeling 3.1 Ramswamy and Anbananthan Model RamswamyandAnbananthan[2]derivedthe modelbasedontheassumptionoflinearityofacoustic impedance with the mole fraction of components. Further it is assumed,thatanequilibriumphysicalpropertysuchas viscosity,refractiveindex,surfacetensionetcwhichare basedonlinearitycanbepredicted[15-19].Glinski[3] assumedthatwhensoluteisaddedtosolventthemolecules interact according to the equilibrium as: A+B = AB (2) andtheassociationconstantKascanbedefinedas; [ ][ ] [ ]a sA BKA B# (3) whereAisamountofsolventandBisamountofsolutein the liquid mixture.Byapplyingtheconditionoflinearityinspeedof sound with compositionuobs = xA uA + xAB uAB(4) where xA, xAB, uA and uAB and uobs are the mole fraction of A, molefractionofassociateAB,surfacetensionofA, ultrasonicvelocityofassociateABandobservedultrasonic velocityrespectively.ThecomponentABcannotbe obtainedinitspureform.Followingsimplificationshave been made, firstly, concentration term should be replaced by activitiesforconcentratedsolutionandsecond,thereare alsomoleculesofnonassociatedcomponentsintheliquid mixture. The eq (4) takes the form, uobs = [xA uA + xB uB + xAB uAB](5) Thegeneralideaofthismodelcanbe,however,exploited as;

]) [ ])( [ (] [AB C AB CABKB Aas" "#(6)whereCA andCBareinitialmolarconcentrationsofthecomponents. One can take any valueof Kas and calculate the equilibrium valueof[AB]for everycompositionof themixtureaswell as[A]=CA-[AB]and[B]=CB-[AB].Replacingmolar concentrationbyactivitiesforconcentrated solution,eq(6)becomes,) )( (AB B AB AABasa a a aaK" "#(7)whereaA,aBandaABaretheactivityofcomponentA, ComponentBandassociate,ABrespectively.Takingequi molar activities which are equal to;and, aA=aA-aAB and aB = aB-aAB whereaAandaBaretheactivitiesof[A]and[B]inequi molar quantities respectively. Fromeq(7)onecanobtainthevalueofKasas; 2AB AB B AB A B AABasa a a a a a aaK$ " "#(8)B AABa aa' . '#

Now,assuminganyvalueofultrasonicvelocityinthepure component AB, uAB, it ispossible to compare the ultrasonic velocitycalculatedusingeq(5)withtheexperimental values.On changingboththeadjustable parameters Kasand uABgradually,onecangetdifferentvaluesofthesumof squares of deviations,S =% (uobs - ucal) 2 (9) whereuobsanducalaretheobservedandcalculated equilibrium properties respectively.TheminimumvalueofScanbeobtained theoretically by a pair of the fitted parameters. But we found that for some Kas and uAB, the value of S is high and changes rapidly,andforothers,itislowandchangesslowlywhen changingthefittedparameters.Insuchcases,thevalueof uABshouldnotbemuchlowerthanthelowestobserved ultrasonicvelocityofthesystemormuchhigherthanthe highest one. Quantitatively, it should be reasonable to accept thepairof adjustableparameters Kas and uABwhichhasthe physicalsenseandwhichreproducestheexperimental physical property satisfactorily.Glisnki[3]improvedtheRamaswamyand Anbananthanmodelbysuggestingtheequationassuming additivity with the volume fraction, & of the components as,1 2 2 12 1u uu uucal# # $# (10)where ucal is thetheoreticalultrasonicvelocityofbinaryliquidmixture, &1, &2 are the volume fractions of component 1 and 2 and u1 andu2aretheultrasonicvelocityofpurecomponent liquids.Thenumericalprocedureanddeterminationof associationconstant,Kas,weresimilartothatdescribed beforeandtheadvantageofthismethodascomparedwith theearlieronewasthatthedataondensitiesofliquid mixturearenotnecessaryexceptthoseofpurecomponents needed to calculate the volume fractions 3.2 Prigogine-Flory-Patterson Model With.theparticular(3,")choiceofm,npotentialorthe Flory model takes the form as; )]0 . 15 . 0ln( )0 . 1( [ ) (3 / 1~3 / 1~~23 / 1~3 / 5~ ~ ~"" "" #"VVVVV M V $(11)ThusonthebasisofFlorytheory,surfacetentionofliquid mixture is given by the expression, ) (~ ~*V $ $ $ #(12)

3 / 2410 3 . 6''()**+,#"!$xu (13)All the notations used in the above equations have their usual significance as detailed out by Flory. 4. Results & Discussion ConsideringvanderWaalsequationofstate,relations betweenassociationphenomenonsinliquidswereanalyzed earlier[16]withoutanalyzingthesystemintermsof R.K.Shukla, International Journal of Latest Research in Science and Technology. ISSN: 2278-5299 462 equilibrium.Theassociationphenomenonhasbeenrelated usuallythedeviationofdifferentquantitiesfromadditivity. RamaswamiandAnbananthanmodelwasfurthercorrected [3]andtested[17]topredicttheassociationalbehaviorof binaryliquidmixtures.Thequantitiesanalyzedwere refractive index, molar volume, viscosity, intermolecular free lengthandmanyothers[17-19].Predictionofultrasonic velocity from this approach is our first attempt. The results of fittingsobtainedfromthemodelwereutilizedproperly.The basicdoubtregardingthismodelexcepttheassumptionof linearity of ultrasonic velocity with mole fraction is that these liquidshavepoor affinityto formdimmers.The calculations wereperformedusingacomputerprogramwhichallows fittingseasilyboththeadjustableparameterssimultaneously or the parameters were changed manually.We constructed thedata sheet in a computer program with associationconstantKasandCA,Basthefittedparameters. CA,BistheultrasonicvelocityinthepurecomponentAB means a hypothetical liquid having only the associate AB. On changing these parameters, the equilibrium concentrations of species[A],[B]and[AB]willchangeandtheultrasonic velocitycanbecomputed.Thedifferencebetween experimentalandtheoreticalvaluesforultrasonicvelocityis used toobtain the sum of squares of deviation.It is assumed that in solution three associates instead of two are formed (A, BandAB).Thevaluesofultrasonicvelocityinpure associate can be treated as a fitted one with the value of Kas.Thermalexpansioncoefficient(-)andisothermal compressibility needed in the PFP model were obtained from the equation which have already been tested in many cases by us [16, 19] and others. Themixingfunction!.canberepresentedmathematically by Redlich-Kister polynomial equation [7] for correlating the experimental data as; iipiix A x x y ) 1 2 ( ) 1 (101" " # /# (14)whereyreferstodeviationinultrasonicvelocity(!u),x1is the mole fraction and Ai is the coefficient MultibodyinteractionmodelofMcAllister[8]is widelyusedforcorrelatingtheviscosityofliquidmixtures withmolefractionwhichisbasedontheassumptionof additivity.Thethreebodymodelforultrasonicvelocityis definedas; b x x a u x u x u ln 3 ln 3 ln ln22 1 221 131$ $ # +)] / [ln( ln1 2 2 1 232M M x x u x $ " (15) $ $ ] 3 / ) / 2 [ln( 31 2 221M M x x) 1 232 1 222 1/ ln( ] 3 / ) / 2 1 ln[( 3 M M x M M x x $ $ and four body model is given by,b x x a x x u x u ln 6 ln 4 ln ln2221 231 141$ $ # (16) + )] / ln( ln ln 41 2 2 1 24232 1M M x x u x c x x $ " $2 / ) / 1 ln[( 6 ] 4 / ) / 3 ln[( 41 22221 1 2 231M M x x M M x x $ $ $ $) 1 242 1 232 1/ ln( ] 4 / ) / 3 1 ln[( 4 M M x M M x x $ $ where u,x1, u1,M1,x2, u2 andM2 are the ultrasonicvelocity of mixture,molefraction,ultrasonicvelocityandmolecular weight of pure component 1 and 2 respectively; a,b and c are adjustableparametersthatarecharacteristicofthesystem. Thecoefficientsa,b,andcwerecalculatedusingtheleast square procedure and the results of estimated parameters and standarddeviationbetweenthecalculatedandexperimental values are presented in Table 3. It is observed that four body modeliscorrelatedthemixtureultrasonicvelocitytoa significantlyhigherdegreeofaccuracyforallthesystems thanthethreebodymodel.GenerallyMcAllistermodelis adequate in correlating the systems having small deviations.Mixture data are presented in Table 4-5. With the increase ofmolefraction,thevaluesofultrasonicvelocityobtained from all the models decrease at all temperatures except at few places.Theabsoluteaveragepercentdeviations(AAPD)in ultrasonicvelocityandisentropiccompressibilityobtained from different models are provided in Table 4. It is observed thatassociatedprocessesprovidefairlygoodresultsas comparedtonon-associated.HigherdeviationvaluesinPFP model can be explained as the model was developed for non-electrolyte0-meric spherical chainmoleculesandthesystem underinvestigationhaveinteractingandassociating properties.Moreover,theexpressionusedforthe computation of - and 1T are also empirical in nature. Positive deviationsinspeedofsoundarearesultofmolecular associationandcomplexformationwhereasnegative deviations are duetomolecular dissociation.The actualsign and magnitude of deviations depend upon relative strength of twooppositeeffect.Thelacksofsmoothnessindeviations aredueto theinteractionbetween thecomponentmolecules. Isentropiccompressibilityincreasesregularlywiththe increaseofmolefractionwhiledensityandultrasonic velocity show regular behavior. Results of ultrasonic velocity obtainedfromdifferentmodelsalongwithpercentdeviation arereportedinTable5.Acarefulperusaloftheresults clearlyindicatesthecloseproximityofourresultswiththe experimental findings.Conclusively,modelsassumingassociatingproperties providemorereliableresultsascomparedtoothermodels having no associating properties andhelpful in deducing the internalstructureofassociatesthroughthefittedvaluesof ultrasonicvelocityandisentropiccompressibilityina hypotheticalpureassociateandobserveddependenceof concentration on composition of a mixture. References [1]R.K.Shukla, S.N.Dixit,Pratima Jain Preeti Mishra andSwetaSharma,UltrasonicVelocityandIsentropicCompressibilityofBinaryFluid Mixtures at 298.15 K.Orbital Elec. J.Chem.2 (2010) 356-364 [2]K.Ramaswamy,D.Anbananthan,Acustica.48(1981)281-282: J.GlinskiDeterminationoftheconditionalassociationconstantsfrom thesoundvelocitydatainbinaryliquidmixtures.J.Chem.Phy.118, (2003) 2301-2307[3]J.Glinski,Determinationoftheconditionalassociationconstantsfrom thesoundvelocitydatainbinaryliquidmixtures.J.Chem.Phy.118 (2003) 2301-2307[4]A. Abe, P.J. Flory, The thermodynamic properties of mixtures of small non-polar molecules. J.Am.Chem.Soc. 82 (1965)1838-1845 [5]I.Prigogine,A.Bellemans,A.Mathod,MolecularTheoryofSolutions, North-Holland, Amsterdam ( 1957)[6]D.Patterson,A.K.Rastogi,Thesurfacetensionofpolyatomicliquids and the principle of corresponding states. J.Phy.Chem. 74 (1970)1067-1071 R.K.Shukla, International Journal of Latest Research in Science and Technology. ISSN: 2278-5299 463 [7]O.Redlich,A.T.Kister,Thermodynamicsofnonelectrolyticsolutions. Algebricrepresentationofthermodynamicpropertiesandthe classification of solutions. Ind. Eng. Chem. 40 (1948) 345-348 [8]R.A.McAllister,Theviscosityofliquidmixtures.AIChEJ.6(1960) 427-431 [9]R.K.Shukla, A. Kumar, K.Srivastava, S.Yadava, A. Comparative Study of PFP and BAB Models In Predicting The Excess Thermo-Acoustical andItsAlliedPropertiesofTernaryLiquidMixturesAt298.15k,J. Molliq. Liq. 140 (2008) 25-32. [10]R.K.Shukla,A.Kumar,N.Singh,A.Shukla,Density,Ultrasonic Velocity,SurfaceTension,ExcessVolumeandViscositiesof Quaternary Fluid Solutions, J. Molliq. Liq. 140 (2008) 117-122. [11]R.K.Shukla,A.Kumar, K.Srivastava,N.Singh,A Comparative Study ofPFPandBABModelsInPredictingTheSurfaceandTransport PropertiesofLiquidTernarySystems,J.Solution.Chem.36(2007) 1103-1116 [12]R.K.Shukla, R.D. Rai, A.K.Shukla, N.Mishra, J. D. Pandey, Ultrasonic andThermodynamicPropertiesofQuaternaryLiquidSystemAt 298.15 K, Indian J. Pure & Appl. Phys. 31(1993) 54-59[13]R.K.Shukla,R.D.Rai,A.K.Shukla,J.D.Pandey,UltrasonicSpeed IsentropicCompressibilityandExcessIsentropicCompressibilityFor Three Ternary Mixtures At 298.15 K, J. Chem. Thermodyn. 21 (1989) 125-129 [14]J.A.Riddick,W.B.Bunger,T.K.Sakano,OrganicSolventsTechniques of Chemistry, 4th Ed. Willey: New York (1986) [15]M.I.Aralaguppi,C.Jadar,T.M.Aminabhavi,Density,viscosity, refractiveindexandsoundvelocityinbinarymixturesof2-chloroethanol with methyl acetate,ethyl acetate, n-propyl acetate and n-butyle acetate. J.Chem.Eng.Data. 44 (1999) 441[16]R.K.Shukla,N.Awasthi,A.Kumar,A.Shukla,V.K.Pandey,PredictionofAssociationalBehaviourofBinaryLiquidMixtures from Viscosity Data J.Molliq. Liq. 158 (2011)131-138[17]A.Ali,M.Tariq,Surfacethermodynamicbehaviorofbinaryliquid mixturesofbenzene+1,1,2,2-tetrachloroethaneatdifferent temperatures:anexperimentalandtheoreticalstudy.Phys.Chem. Liq. 46 (2008) 47-58[18]A.Rodrignez,J.Canosa,J.Tojo,Density,refractiveindexandspeed of sound of binary mixtures (diethyl carbonate + alcohols) at several temperatures. J.Chem.Eng.Data. 46 (2001) 1506[19] I.Prigogine,L.Saraga,Test ofmonolyermodelforsurfacetension of simple liquids. J.Chem. Phys. 49(1952) 399-407 [20]R.K.Shukla, Atul. Kumar, Kirti. Srivastava, Neetu. Singh,A comparativestudyofthePFPandBABmodelsinpredictingthe surfaceandtransportpropertiesofliquidternarysystems.J. Solution. Chem., 36 (2007) 1103-1116 Table1ComparisonofDensityandSoundVelocitywithliteraturedataforpurecomponentsat293.15,298.15, 303.15, 308.15 and 313.15 K Compound T ! x 10-3 K T/TPa-1

V/cm3 mole-1 "exp/ g.cm-3 "lit/ g.cm-3 uexp/ ms-1 ulit/ ms-1 Acetonitrile293.151.2762108.8451.530.7865 0.7822 1305.5 1347.1 298.151.2943113.5452.550.7811 0.77649 1290.1 1326.3 303.151.3151119.1053.080.7733 0.77125 1263.4 1293.4 308.151.3300123.1853.550.7665 - 1245.1 1263.5 313.151.3420126.5453.970.7605 - 1230.5 1242.7 Formamide293.150.943143.9239.781.1320 1.1339 1625.8 1647.9 298.150.951545.1139.891.1290 1.12915 1601.0 1626.3 303.150.957045.8940.031.1250 - 1585.2 1607.2 308.150.959446.2440.171.1210 1.12068 1577.2 1585.1 313.150.965647.1540.511.1117 - 1565.1 1571.3 Table 2 Coefficients of the Redlich-Kister Equation and Standard Deviations (#) for Speed of Sound andAdiabatic Compressibility of Binary Liquid Mixtures at Various Temperatures. acetonitrile+formamideSpeed of Sound (u/ms-1)Isentropic compressibility (s/TPa-1)TA0A1 A2 A3Std dev(#) A0 A1 A2 A3Std dev(#) $u293.15 129.76-436.4788.41828.426.54$s136.10-430.00583.00490.006.12 298.15 306.98-155.980.48399.8710.26-521.40-61.00-230.00-620.00 7.80 303.15 -82.22-31.92-574.12-578.7413.77-323.00-160.00492.00686.0012.00 308.15 311.86667.97-239.85-1276.315.40-576.40-800.00189.00126.0019.00 313.15 222.1916.82-140.61-151.849.69-498.40-190.0026.50122.0011.00 Table 3 Parameters of McAllister Three body and Four body Interaction Models and Standard Deviations (#) for Speed of SoundofBinary Liquid Mixtures at Various Temperatures. McAllister Three Body (u/ms-1) McAllister Four Body(u/ms-1) Component Tempax10-3b x10-3(#)a x10-3b x10-3c x10-3 (#) Acetonitrile+ Formamide 293.15 1.4171.62213.10 1.4031.4851.64313.11 298.15 1.5021.60410.06 1.4531.5381.61210.06 303.15 1.2321.52418.09 1.1561.5611.42524.08 308.15 1.5361.48117.85 1.4251.5721.46720.29 1.5551.48216.231.4611.5281.49616.28 R.K.Shukla, International Journal of Latest Research in Science and Technology. ISSN: 2278-5299 464 Table 4 Comparison of Average Absolute Percentage Deviation (AAPD) values obtained from variousliquid state models acetonitrile+formamide Temperature Kasu ab /ms-1 uPFP/ ms-1 AAPD uRS/ ms-1 AAPD uGlinski /ms-1 AAPD uMacAllister 3-body /ms-1 AAPD uMacAllister 4-body /ms-1 AAPD sPFP/ TPa-1 AAPD s RS/ TPa-1 AAPD sGlinski/ TPa1 AAPD 293.150.00011350.008.141.743.570.820.8318.753.617.62 298.150.00011355.009.103.755.560.590.5921.308.0112.26 303.150.00011360.003.21-2.8612.390.981.116.645.433.01 308.15 0.00011365.005.953.37-16.390.921.1213.1111.9620.38 313.150.00011370.003.934.31-0.010.920.938.425.1116.67 Table5ExperimentalDensities("),ExperimentalUltrasonicVelocity(uExp),TheoreticalUltrasonicVelocity (uTheo),obtainedfromPrigogine-Flory-Pattersonmodels,Ramaswamy&Abnananthanmodel,modeldevisedby Glinski,deviationsinUltrasonicVelocity(u)anddeviationinAdiabaticCompressibility(!)ofBinaryLiquid Mixtures at various temperatures. acetonitrile+formamide x1 / g.cm-3 uExp (m/s) u PFP (m/s) uRS (m/s) uGlinski (m/s) %!PFP%!RS %!Glinski sExp (TPa-1) % sPFP (TPa-1) % s RS (TPa-1) % sGlinski (TPa-1) 293.15 0.12251.12581605.81475.51586.51566.98.111.192.41344.474-18.44-2.44-5.02 0.2391.09921585.61431.31549.21518.19.722.294.25361.856-22.71-4.75-9.09 0.34991.08351575.91383.11513.61476.912.23.946.27371.633-29.81-8.39-13.84 0.45571.04051525.91363.01479.71441.810.63.025.51412.768-25.33-6.33-12.00 0.55671.01021469.81336.11447.41411.39.091.523.97458.222-21.01-3.11-8.45 0.65330.97051425.81321.31416.51384.87.320.652.87506.859-1.32-6.01 0.74560.94031386.91301.71386.91361.46.13-0.001.83552.896-13.500.01-3.77 0.8340.90151375.31293.51358.61340.65.941.212.51586.461-13.03-2.47-5.23 0.91870.85031355.91301.41331.51322.14.011.792.48639.694-8.54-3.69-5.17 298.15 0.12251.10151590.61484.41562.81543.26.671.742.97358.834-14.81-3.58-6.23 0.2391.08251583.61432.21526.61495.59.553.595.55368.367-22.25-7.60-12.12 0.34991.06571576.91383.91492.11455.512.295.377.69377.360-29.84-11.68-17.37 0.45571.03451535.81352.91459.21421.311.904.987.44409.826-28.86-10.76-16.75 0.55670.99851490.51330.51427.81391.910.734.206.61450.804-25.50-8.96-14.66 0.65330.96241476.91312.21397.81366.311.145.357.48476.367-26.67-11.63-16.84 0.74560.93511409.21289.71369.11343.88.472.844.64538.513-19.38-5.93-9.97 0.8340.87921389.81297.81341.61323.86.613.464.74588.854-14.67-7.30-10.21 0.91870.84921345.91284.81315.31306.04.532.262.95650.076-9.72-4.70-6.19 303.15 0.12251.09981525.91478.81545.71524.53.08-1.303.33390.511-6.472.55-0.17 0.2391.07351498.21431.11508.21474.84.47-0.676.49415.009-9.591.33-3.20 0.34991.05381456.81383.41472.51433.25.03-1.089.12447.138-10.892.13-3.32 0.45571.02581402.51348.01438.51397.93.88-2.5611.36495.600-8.254.94-0.66 0.55670.98021367.51332.81406.01367.62.53-2.8113.28545.545-5.275.400.02 0.65330.95941335.81299.41374.91341.22.72-2.9214.95584.140-5.675.610.81 0.74560.92561290.51281.61345.21318.10.68-4.2416.42648.725-1.387.974.16 0.8340.87281259.81285.71316.71297.8-2.0-4.5217.71721.9084.008.475.77 0.91870.84021220.21274.31289.51279.6-4.43-5.6818.86799.3838.3110.479.08 308.15 0.12251.08561555.81490.91519.41288.44.162.33-4.71380.559-8.89-4.85-45.80 0.23901.05681525.81443.51468.81329.25.393.73-8.02406.454-11.72-7.91-31.75 0.34991.02151490.51408.01424.71367.75.524.41-11.1440.654-12.05-9.45-18.76 0.45570.98561485.91378.51386.21404.07.226.70-14.10459.536-16.18-14.89-12.01 0.55670.95081475.91352.81352.91438.38.338.33-16.88482.833-19.02-19.00-5.29 0.65330.92561456.81322.31324.11470.89.239.10-19.53509.069-21.38-21.041.90 0.74560.88091399.81314.71299.31501.66.077.17-22.03579.350-13.36-16.0613.10 0.83400.84051366.91307.31278.11530.84.356.49-24.41636.779-9.32-14.3720.28 0.91870.80281260.81301.21260.21558.7-3.200.04-26.67783.6106.12-0.0934.57 313.15 0.12251.08071543.81488.51524.01397.33.572.0312.15388.251-7.55-2.60-22.06 0.2391.05591525.81437.21485.11422.35.802.6610.18406.801-12.71-5.56-15.08 0.34991.01581490.51405.81447.91445.25.672.858.34443.126-12.40-5.96-6.36 0.45570.97581475.81379.91412.51466.46.494.934.51470.526-14.37-9.15-1.28 0.55670.93651425.61358.41378.71485.94.716.570.30525.408-10.13-6.917.96 0.65330.89051382.51348.31346.41504.12.477.57-1.84587.537-5.13-5.4215.52 0.74560.87261364.81314.31315.51520.93.696.01-7.93615.243-7.82-7.6219.48 0.8340.84051300.81298.31286.01536.60.185.91-10.56703.139-0.38-2.3128.34 0.91870.79921260.81295.71257.61551.3-2.770.24-15.26787.1405.33-0.4933.95