CHAPTER-2 LITERATURE REVIEW

Transcription

1 CHAPTR-2 LITRATUR RVIW 37

2 2.1 Review o previous work In the literature o solution chemistry, the thermodynamic, acoustic, transport, and optical properties o liquid-liquid mixtures constitute an important area o research. In the last two decades, much work has been done on the study o densities, speeds o sound, viscosities, and reractive indices o the binary liquid mixtures containing alcohols but it is beyond the scope o this thesis to give an entire coverage o the published work. Only the representative papers dealing with binary mixtures o alcohols with alkane, haloalkanes, methyl methacrylate, acetonitrile, ethylacetate and ethenyl ethanoate will be cited. However, in the present thesis, emphasis will be given on the measurement o our physical properties, viz. density, speed o sound, viscosity, and reractive index o the binary liquid mixtures o aromatic hydrocarbons with higher alcohols. Using this data, the mixing quantities have been evaluated to investigate their eect in terms o the binary interactions. Literature survey indicates that not much work has been carried out on the study o thermodynamic, acoustic, transport and optical properties o binary mixtures o aromatic hydrocarbons with higher alcohols. The variations in the volumetric and acoustic properties o binary mixtures o alcohols containing alkane, haloalkanes, methyl methacrylate, acetonitrile, ethylacetate and ethenyl ethanoate, with the molecular size, shape, chain-length and degree o molecular association o normal alcohols and branched alcohols have been reported earlier [18-28, ]. Mehdi Hasan et al. [133] measured the density ( ) o the binary liquid mixtures o methylbenzene with higher branched alcohols Cn H 2n 1OH (n = 6 and 8) at K. These measurements were used to compute the excess molar volumes ( V ) o these binary liquid mixtures. V. K. Ratan and anchita Chauhan [134] measured the density ( ) o the binary liquid mixtures o benzyl acetate with dichloromethane and branched alcohols Cn H 2n 1OH (n = 4 and 8) at , , , and K. These measurements were used to compute the excess molar volumes ( V ) o these binary liquid mixtures. 38

3 . L. Oswal et al. [135] measured the density ( ) and speeds o sound o the binary liquid mixtures o alkanol with cycloalkane and methylcyclohexane and alkan-2-ol with cyclohexane at K. These measurements were used to compute the excess molar volumes ( V ) o these binary liquid mixtures. Brown et al. [136,137] measured the density ( ), o the binary liquid mixtures o benzene with lower alcohols Cn H 2n 1OH (n = 1 to 5) at K. These measurements were used to compute the excess molar volumes ( V 39 ), o these binary liquid mixtures. Rodriguez et al. [138] measured the excess molar volumes ( V ), o the binary mixtures o benzene with 1-butanol at K. Ortega and Paz Andrade et al. [ ] measured the excess molar volumes ( V ) o the binary mixtures o benzene with 1-pentanol at and K, with 1-hexanol at K and with 1-heptanol at to K. Chun-Hung Yu and Fuan-Nan Tsai [142] measured the excess molar volumes ( V with C H 2n OH (n = 4 to 10) at and K. n 1 ) o the binary mixtures o benzene Kijevanin et al. [143] measured the densities ( ), o the binary and ternary systems o methanol with benzene and chloroorm at , , , , and K at atmospheric pressure with an Anton Paar DMA 5000 vibrating tube densimeter. xcess molar volumes ( V ), were correlated by the Redlich Kister (or binary systems) and Nagata Tamura (or ternary systems) equations. erbanovic et al. [144] studied the densities ( ), o the ternary systems o methanol with benzene, chlorobenzene; and the densities o ethanol with benzene and chlorobenzene binary liquid mixtures at , , , , and K and at kpa. xcess molar volumes ( V ) were determined and itted to the Redlich Kister equation. The values o limiting excess partial molar volumes ( V i ), were also calculated. The results have been analyzed in terms o speciic molecular interactions present in these mixtures taking into consideration the eect o temperature on them. The correlation o V binary data was perormed with the Peng Robinson tryjek Vera cubic equation o state (PRV CO) coupled with the van der Waals and CO/G mixing

4 rules introduced by Twu Coon Bluck Tilton [145]. The experimental values o V were compared with those estimated by both the mixing rules at the temperature range, and on each temperature, separately. The densities ( ) o the binary liquid mixtures o ethanol with benzene, and ternary systems o ethanol with benzene and 2-butanone were measured by Grguric et al. [146] at K and at atmospheric pressure. The excess molar volumes ( V ) were calculated and itted to the Redlich Kister equation or binary and ternary mixtures and the V data o these liquid mixtures were correlated by the van der Waals and Twu Coon Bluck Tilton [145] mixing rules coupled with the Peng Robinson tryjek Vera equation [147] o state. ( V K. N. Marsh and Carol Buritt [148] determined the excess molar volumes ) o ethanol with benzene, p-xylene, cyclohexane, n-hexane, carbon tetrachloride and cyclopentane at to K. The unsymmetrical, with the unction V 40 V values are highly /x (1 x) showing a very rapid increase at low mole ractions o ethanol. The limiting partial molar excess volumes o ethanol in the various non-polar solvents show a similar trend to that observed or the limiting partial molar excess enthalpy o ethanol in the same solvents. Kijevanin et al. [149] measured the densities ( ) and excess molar volumes ( V ) o the benzene with 1-propanol and their ternary mixtures o 1- propanol with chloroorm and benzene. xperimental measurements were perormed at , , , , and K at atmospheric pressure with an Anton Paar DMA 5000 digital vibrating tube densimeter. The V values were itted to Redlich Kister (or binary systems) and Nagata Tamura (or ternary systems) equations. Thirumaran et al. [150] studied the speed o sound (u ), densities ( ) and viscosities ( ) or the binary mixtures o 1-propanol with benzene, toluene and cyclohexane at K. The experimental data were used to calculate the acoustical parameters, namely adiabatic compressibility ( ), ree length ( L ), ree volume ( V a ), acoustic impedance ( Z ) and excess molar volume ( V ). A weak molecular interaction between the component molecules has been observed

5 in these systems. Also, addition o non-polar component to polar 1-propanol causes the dissociation o its hydrogen bonded structure. The densities ( ), viscosities ( ) and reractive indices ( n D ) o binary mixtures o benzene with isomeric butanol (1-butanol, 2-methyl-1-propanol, 2- butanol and 2-methyl-2-propanol) were measured over the complete composition range at 30 0 C by Ali et al. [151]. The experimental data were used to calculate the excess molar volume ( V ), deviation o viscosity ( ), deviation o reractive index ( ) and apparent molar volume ( V 0 i ) at ininite dilution. The variation o nd this parameter with composition and the eect o branching in alcohols have been discussed rom the point o view o intermolecular interaction in these mixtures. mixtures o miljanic et al. [152] measured the densities ( ) o the binary liquid 1-butanol + benzene, 1-butanol + chloroorm and their ternary mixtures o 1-butanol + chloroorm + benzene at , , , , and K at the atmospheric pressure, using an oscillating U- tube densimeter. From these densities ( ), the excess molar volumes ( V 41 ) were calculated and itted to the Redlich Kister equation or all the binary mixtures and to the Nagata and Tamura equation or the ternary systems. The Radojkovic et al. equation was used to predict the V o the ternary mixtures. Also, V data o the binary systems were correlated by the van der Waals (vdw) and Twu Coon Bluck Tilton [145] mixing rules coupled with the Peng Robinson tryjek Vera equation [144] o state. The prediction and correlation o systems were perormed by the same models. V data or the ternary Rodriguez-Nunez and Ortegab [153] studied the densities ( ), viscosities ( ) and reractive indices ( n D ) o binary mixtures o benzene with 1-butanol, 2- methyl-1-propanol, 2-butanol and 2-methyl-2-propanol over the complete composition range at 30 C. The experimental data were used to calculate excess molar volumes ( V ), viscosity deviations ( ), excess ree energies o activation o viscous low ( G * ), reractive index deviations ( nd ), apparent molar volumes ( V 0 i ) and partial molar volumes ( V i ) o benzene in alcohols and alcohols in benzene, respectively, at ininite dilution. The variations o these parameters with

6 composition and the eect o branching in alcohols have been discussed rom the point o view o intermolecular interactions in these mixtures. Densities ( ) and excess molar volumes ( V ) o the ternary mixtures o 2-butanol + chloroorm + benzene and binary mixtures o 2-butanol + chloroorm and 2-butanol + benzene, were determined by miljanic et al [154]. xperimental densities ( ), measurements were perormed at , , , , and K, and at the atmospheric pressure with an Anton Paar DNA 5000 digital vibrating tube densimeter. xcess molar volumes ( V ), were correlated by the Redlich Kister equation or binary mixtures and the Nagata Tamura equation or ternary mixtures. Densities ( ), speeds o sound ( u ) and viscosities ( ) o the binary mixtures o toluene with methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1- ol and 2-methylpropan-2-ol were measured at , and K or these binary liquid mixtures or the whole composition range by Nikan et al. [155,156]. Hasen et al. [157,158] measured the densities ( ), speeds o sound ( u ) and viscosities ( ) o the binary mixtures o toluene with heptan-1-ol, octan-1-ol and decan-1-ol at to K. xcess molar volumes ( V ), deviation in isentropic compressibilities ( ) and viscosity deviations ( ), were calculated and correlated by Redlich-Kister type unction to determine the itting parameters and the standard deviations. The Jouyban-Acree model was used to correlate the experimental values o densities ( ), speeds o sound (u ) and viscosities ( ) at dierent temperatures. The excess molar volumes ( V ), at K were obtained as a unction o mole raction x or the binary liquid mixtures o o-xylene with n-alkanol, (n = 6, 7, 8); and m-xylene and p-xylene with n-alkanol, (n = 3, 4, 5, 6, 7, 8); using a vibrating-tube digital densimeter by Rodriguez-Nuneza et al. [159]. Gopal and Prabhakara Rao [160] studied density ( ) and the speed o sound (u ) o decan-1-ol with benzene, toluene, o-xylene, m-xylene, p-xylene and ethylene at K. The data were used to calculate isentropic compressibilities 42

7 ( ), intermolecular ree length ( ' speed ( R ) and van der Waals constant ( b ). with m L ), relative association ( R A ), molar sound Densities ( ) and speed o sound ( u ) o binary mixtures o ethylbenzene hexan-1-ol, heptan-1-ol, octan-1-ol and decan-1-ol were measured over the entire range o composition at K and at the atmospheric pressure by Dewan et al. [161,162]. From the experimental values o density ( ) and speed o sound (u ), the excess molar volumes ( V ), isentropic compressibilities ( ), intermolecular ree length ( speed ( L ), relative associations ( R A ), molar sound R m ), excess ree volumes ( V ) and van der Waals constants ( ' b ) were calculated. The speeds o sound or all the binary liquid mixtures were also calculated at dierent concentrations using Flory s theory, Jacobson s ree length theory, chaas collision actor theory, Junjie s empirical relation and Nomoto s relation. Densities ( ), or binary mixtures o 1,2,4-trimethylbenzene with 1- butanol, 2-methyl-1-propanol, 2-butanol, and 2-methyl-2-propanol and the binary liquid mixtures o 1,3,5-trimethylbenzene with 1-butanol, 2-methyl-1-propanol, 2- butanol, and 2-methyl-2-propanol were determined over the entire concentration range at K by Ouyang [163], and excess molar volumes ( V ), were derived. urace tensions o these binary mixtures were measured at K by the pendant drop method, and the values o the surace tension deviation or these mixtures were also calculated. Palaiologou [164] studied the excess molar volumes ( V ) and isentropic compressibilities ( ), o binary mixtures o m-chlorotoluene with 2-propanol, 2- methyl-1-propanol and 3-methyl-1-butanol at K. The V values are algebraically smaller than those or the mixtures which include toluene in place o m-chlorotoluene. The deviation in isentropic compressibility ( ), is negative over the whole range o composition in the three mixtures. This deviation is algebraically smaller than that observed or the mixtures o these three alcohols with toluene. 43

8 Naidu et al. [165] measured the densities ( ) and speed o sound ( u ) o binary mixtures o p-chlorotoluene with 2-propanol, 2-methyl-l-propanol and 3- methyl-1-butanol at K. The results o excess molar volumes ( V isentropic compressibilities ( ) and ) were compared with those o the three corresponding 1-alkanols. Deviation in isentropic compressiblility ( ), the dierence between the value o the unction or the real mixture and that or the ideal mixture, is negative over the whole range o composition in the three mixtures. Kumar and Naidu [166] studied the excess molar volumes ( V ) o p- chlorotoluene with 1-propanol, 1-butanol, 1-pentanol, 1-hexanol and 1-heptanol at K. The V values are negative or mixtures rich in alkanol and positive or those rich in p-chlorotoluene. A comparison o these results with those or the mixtures o these alkanols with toluene shows that the algebraic values o excess molar volumes ( V ) are smaller in the ormer group. The V values or the ternary mixtures o p-chlorotoluene and n-hexane with 1-alkanols were calculated at K. The experimental results have been compared with those predicted by empirical equations using the binary data. xcess enthalpies ( H ), o binary mixtures containing poly(propylene glycols) o dierent molecular masses with m-cresol and anisole were determined using a low microcalorimeter at K and at atmospheric pressure by Comelli and Ottani [167]. The excess quantities have been correlated using the Redlich Kister polynomial equation. Results have been qualitatively discussed in terms o molecular interactions and o the regular solution model. Densities ( ) and viscosities ( ) or the m-cresol with (ethylene glycol or methanol) binary systems have been experimentally determined over several temperatures and at normal atmospheric pressure, over the entire mole raction range by C. Yang et al [168]. Other mixing properties o interest such as the excess molar volumes ( V ), and the viscosity deviations ( ), have been also obtained or each o the systems. 44

9 Density ( ), viscosity ( ) and reractive index ( n D ) values o anisole with hexane, or heptane, or octane, or nonane, or decane, or dodecane binary mixtures over the entire range o mole raction at , , and K, were investigated at the atmospheric pressure by Al-Jimaz and Al-Kandary et al [169]. The excess molar volume ( V ) were calculated rom the experimental measurements. These results were itted to Redlich-Kister polynomial equation to estimate the binary interaction parameters. The viscosity data ( ) were correlated using Grunberg and Nissan, and McAllister equation. The reractive index data ( n D ) were used to calculate the speciic reractivity, and also correlated with Lorentz Lorenz equation. While the negative, and anisole with heptane are sigmoidal, the V values o anisole with hexane are V values or the remaining binary mixtures are positive. The eects o n-alkanes chain length as well as temperature on the excess molar volumes have been studied. These data have been qualitatively used to explain the intermolecular interactions between the mixing components. Nayak and Aralaguppi [170] studied the speeds o sound ( u ), densities ( ), and reractive indices ( n D ) o anisole with benzene, toluene, n-hexane, cyclohexane, 1-butanol and 1-pentanol at 298:15 K and at the atmospheric pressure over the whole concentration range. The corresponding excess properties were computed rom the experimental data using the Redlich Kister equation. Dierent estimative methods were applied and qualitative agreement between the experimental and theoretical values both in magnitude and sign was obtained with Weng [171] measured the densities ( ) and viscosities ( ) or anisole 2-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol binary liquid mixtures with a vibrating-tube densimeter and Cannon-Fenske routine viscometers over the temperature range between and K and at the atmospheric pressure. xcess molar volumes ( V ) and viscosity deviations ( ) were calculated at various temperatures. Both excess molar volumes and the viscosity deviations are negative or all the investigated systems. The isothermal excess molar volumes ( V ) and viscosity deviations ( ) were itted to a 45

10 Redlich-Kister type equation, and the kinematic viscosity data were correlated with the McAllister equation. Densities ( ) and viscosities ( ) were measured or the binary mixtures o anisole with 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol and 3-methyl-2-butanol at , and K over the entire composition range by Weng et al [172]. The excess volumes ( V viscosity deviations ( ) and ) were calculated rom the experimental data and correlated by a Redlich-Kister type equation. McAllister s three-body and ourbody interaction models were also used to correlate the kinematic viscosities. Dielectric study o anisole has been carried out by mixing it with 2-ethyl-lhexanol and decyl alcohol at dierent temperatures by Parthipan and Thenappan [173]. The Kirkwood correlation actor, the excess dielectric permittivity, Bruggeman parameter and the thermodynamic properties o the mixtures have been determined and the results have been interpreted in term o intra- and intermolecular interactions. The interaction between the like molecules is explained with the Kirkwood correlation parameter and the interaction between the unlike molecules is identiied by the excess parameters and Bruggemann parameter. Values o Kirkwood correlation actor, excess static permittivity, Bruggeman parameter and the thermodynamic parameters are ound to depend on the concentration and temperature o the mixtures. The parallel and antiparallel orientations among the dipoles have been analyzed. Joshi [174] studied the excess volume ( V ), excess viscosity ( ), excess ree energy o activation o low ( G* ) and contact interaction parameter or binary liquid mixtures o anisole with methanol or benzene rom densities and viscosities measured at , , and K over the entire mole raction range. The results have been discussed in terms o speciic type o interactions between anisole and methanol. The interactions between anisole and benzene are somewhat less speciic. Auslaender and Heric viscosity models reproduce the experimental viscosities better than the equation o McAllister. 46

11 xcess molar enthalpies ( H ), o binary mixtures o 1-octanol with ethylbenzene, ethyl benzoate, acetophenone, anisole and methanol have been measured at K under atmospheric pressure using an isothermal microcalorimeter by Jung Lien et al. [175]. The experimental 47 H values are positive or all the binary mixtures over the entire compositions range. The experimental data were correlated with the modiied Redlich-Kister polynomial equation. The results have been qualitatively interpreted in terms o thermodynamic molecular interactions between the mixing components. xcess molar volumes ( V ) or the binary mixtures o 1,3- dichlorobenzene and 1,2,4-trichlorobenzene with l-butanol, l-pentanol, 1-hexanol, 1-heptanol and 1-octanol have been determined at K by Naidu et al. [176]. The V values are negative in mixtures rich in alcohols and positive in mixtures rich in 1,3-dichlorobenzene. Isentropic compressibilities ( ), excess isentropic compressibilities ( ), excess molar volumes ( V ), viscosity deviations ( ) and speed o sound D deviations ( u ) or chlorobenzene + 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol and 1-decanol binary mixtures at to K and at the atmospheric pressure were derived rom experimental viscosity ( ), density ( ), and speed o sound ( u ) data by Adel. Al-Jimaz et al. [177]. The calculated excess and deviation unctions were urther itted to the Redlich-Kister polynomial relation to estimate the coeicients and the standard errors. While the experimental viscosity ( ) data was compared with the predicted values obtained rom empirical expressions, the speed o sound ( u ) data was analyzed in term o chaas collision actor theory and Jacobson s intermolecular ree length theory o solutions. The eects o n-alkan-1-ol chain length as well as temperature on the excess molar volumes were studied. Pandey and anguri [178] employed Flory s statistical theory or the computation o speed o sound ( u ), density ( ), internal pressure (P i ), thermal expansion coeicient ( ), isothermal compressibility ( compressibility ( ), heat capacity at constant pressure ( C P T ), adiabatic ), heat capacity at

12 constant volume ( C ), heat capacities ratio (γ), pseudo-gruneisen parameter (Г), V excess volume ( V ) and excess heat capacity at constant pressure ( C P) at varying temperatures or 10 binary and 5 ternary systems. The binary systems investigated were: acetonitrile + benzene, benzene + DMF, acetonitrile + DMF, cyclohexanol + cyclohexane, piperidine + tetrahydropyran, piperidine + cyclohexane, tetrahydropyran + cyclohexane, benzene + p-xylene, benzene + p-dioxane, acetone + methyliodide and the ternary systems are: benzene + chloroorm + cyclohexane, toluene + chloroorm + cyclohexane, chlorobenzene + chloroorm + cyclohexane, dioxane + chloroorm + cyclohexane and chlorobenzene + cyclohexane + n-heptane. The results o calculations show that or all the studied systems, the calculated values o various thermodynamic parameters show the same trend as observed experimentally. Fairly good agreement is ound between theoretical and experimental values. The speed o sound o liquid mixtures was obtained using the most popular Flory theory without the help o any empirical relation. Pandey et al. [179] employed a modiied Flory theory along with the Auerbach and Altenberg relations or the computation o speed o sound o three quaternary liquid mixtures and a comparative study o all the three relations has been carried out. Available volumes ( V a ), o pure liquids and their binary liquid mixtures at varying temperatures have been computed by Pandey et al. [38] using thermoacoustical parameters and the values thus obtained have been compared with the values obtained rom a thermodynamic relation o the available volume. Fairly good agreement between the values obtained rom the two methods proves the applicability o thermoacoustical parameters or the computation o the available volume in pure liquids and their liquid mixtures. Pandey et al. [180] evaluated the intermolecular ree-length ( L ), by making use o thermoacoustical parameters ollowed by a comparative study. To achieve this objective, thermoacoustical parameters o our ternary and two quaternary liquid mixtures have been computed. These parameters have been 48

13 utilized to calculate the available volume ( V a ), which, in turn, has been used to compute intermolecular ree-length ( L ), or the investigated systems. The computed values o L have been compared with the values estimated rom well established thermodynamic and ultrasonic methods. This investigation is a pioneering attempt in the evaluation o intermolecular ree-length involving multicomponent liquid mixtures by making use o thermoacoustical parameters. R. Mehra et al. [181] determined the values o speed o sound (u), density ( ) and viscosity ( ) at three dierent temperatures viz , and K to compute the derived parameters. The excess / deviation parameters calculated are excess molar volume ( V ), excess molar ree volume ( V ), deviation o intermolecular ree length ( ), excess molar isentropic compressibility ( K, ), L deviation o viscosity ( ), deviation o acoustic impedance ( Z ), deviation o D sound speed ( u ), excess internal pressure (π i ), excess enthalpy ( H ) and excess Gibb s ree energy o activation o viscous low ( G* ). The sign and magnitude o these excess and deviation unctions provide detailed inormation about the type and extent o intermolecular interactions over the entire composition and temperature range. These excess parameters were itted to Redlich Kister polynomial equation to get inormation about the standard deviations. The sound speed in ternary mixtures has been predicted using various empirical, semi- empirical and statistical theories. These theories include Nomoto s relation (N), ree length theory (FLT), impedance dependence relation (IDR) and Vandeal- Vangeel ideal mixing relation (VD). These theories were applied to investigate their applicability or the system over the entire composition range at three dierent temperatures. Methyl methacrylate (MMA) is an important monomer attracting the attention o industrialists and scientists because o its various applications and reactivity [182]. The knowledge o thermodynamic and transport properties o MMA in alcohols and other organic solvents is useul in industrial processes. Ultrasonic and viscometric parameters oer simple, easy and accurate ways or m 49

14 calculating several physical parameters which throw light on the molecular interactions in solutions. In this paper, the interactions o two alcohols, tertbutanol and iso-butanol with MMA have been reported, and comparison has been made on the interactive nature o the two alcohols. Computations o ree volume, internal pressure and excess ree volume have been made over the entire concentration range. xistence o mesomeric eects o MMA is clearly seen and the role o structure o alcohols has also been observed. Prompted by the observation that recent literature displays marked disagreement as to the proper treatment o data on the reractive indices o binary liquid mixtures, Brocos [183] clariied the relationship between reractive index and molar volume and the corresponding mixing properties. It has been shown that the reractive index deviation unction must be calculated on a volume raction basis, which makes it directly interpretable as a sign-reversed measure o the deviation o reduced ree volume rom ideality. Densities ( and speeds o sound (u ), o the binary liquid mixtures o tetrahydrouran (THF) with 1-butanol and tert-butanol at K over the entire composition range were measured by Ali and Nain [184]. From these data, isentropic compressibility ( ), intermolecular ree length ( L ), relative association ( R ), acoustic impedance ( Z ), molar sound speed ( R ), deviations A o isentropic compressibility ( ) and excess molar volume ( V ), were calculated. The variation o these parameters with composition o the mixtures helps in understanding the nature and extent o interaction between unlike molecules in the mixtures. Further, theoretical values o ultrasonic speed were evaluated using various theories and empirical relations. The relative merits o these theories and relations have been discussed. The speeds o sound o binary liquid mixtures o 1,1,2,2-tetrachloroethane with benzene, toluene, p-xylene, acetone and cyclohexane were evaluated at and K by Pandey et al. [185] using chaas collision actor theory (CFT), Jacobson s ree length theory (FLT), Nomoto s relation and Van Dael ideal mixing relation. The ideal mixing relation gives the minimum m 50

15 deviation or all the systems except with acetone. The intermolecular ree length ( L ), has also been evaluated using ultrasonic and thermodynamic methods and the limitations o both the methods have been discussed. The deviations o ultrasonic speed and intermolecular ree length have been discussed in terms o weak interaction between unlike molecules. Densities, speeds o sound, and isentropic compressibilities were evaluated or binary mixtures o 1,2-ethanediol with 2-ethyl-1-hexanol, 1-heptanol, or ethanol at the temperature K and densities were evaluated or mixtures o 1,2-ethanediol with 1-nonanol at the temperatures ( and ) K by. Zorebski, A. Kulig [186] In the present thesis, emphasis has been laid mainly on the measurements o our physical properties, viz., density, speed o sound, viscosity and reractive index o the binary mixtures o aromatic hydrocarbons with higher alkanols. Using these data, the other mixing quantities have been evaluated. The Flory and Progogine-Flory-Patterson theories have been applied to analyze the excess molar volumes (V ). The experimental speeds o sound have been analyzed in terms o Nomoto (N), Van Dael (VD), Jacobson s ree length theory (FLT), chaas collision actor theory (CFT), Junjie relation (JN) and Progogine-Flory-Patterson (PFP) Theory. The viscosity data have been correlated using Kendall-Monroe, Grunberg-Nissan, Tamura-Kurata, Hind-Mclaughlin Ubbelohde, Katti-Chaudhary and McAllister s three-body interaction model at dierent temperatures. The experimental reractive indices and molar reractions have been analyzed in terms o various mixing rules viz., Lorentz-Lorenz (LL), Gladstone-Dale (GD), Arago- Biot (AB), Laplace (LP), ykman (K), Wiener (W) and Heller (H) relations. Relative merits o these mixing rules have been discussed in terms o root mean square deviations (RMD). Finally, a linear relation between vander Waals ' parameter ( b ) and molar reraction ( R ) has been provided. Using this equation ' and the knowledge o the value o van der Waals parameter ( b ), the molar reraction ( R ) has been computed and the reractive indices have been predicted in terms o root mean square deviations (RMD). 51