Excess molar heat capacities and excess molar volumes of some mixtures of propylene carbonate with aromatic hydrocarbons

Excess molar volumes V ^E and excess molar heat capacities C _P ^E at constant pressure have been measured, at 25°C, as a function of composition for the four binary liquid mixtures propylene carbonate (4-methyl-1,3-dioxolan-2-one, C₄H₆O₃; PC) + benzene (C₆H₆;B), + toluene (C₆H₅CH₃;T), + ethylbenzene (C₆H₅C₂H₅;EB), and + p-xylene (p-C₆H₄(CH₃)₂;p-X) using a vibrating-tube densimeter and a Picker flow microcalorimeter, respectively. All the excess volumes are negative and noticeably skewed towards the hydrocarbon side: V ^E (cm³-mol^–1) at the minimum ranges from about –0.31 at x₁=0.43 for {x₁C₄H₆O₃+x₂p-C₆H₄(CH₃)₂}, to –0.45 at x₁=0.40 for {x₁C₄H₆O₃+x₂C₆H₅CH₃}. For the systems (PC+T), (PC+EB) and (PC+p-X) the C _P ^E s are all positive and even more skewed. For instance, for (PC+T) the maximum is at x _1,max =0.31 with C _P,max ^E =1.91 J-K^–1-mol^–1. Most interestingly, C _P ^E of {x₁C₄H₆O₃+x₂C₆H₆} exhibits two maxima near the ends of the composition range and a minimum at x _1,min =0.71 with C _P,min ^E =–0.23 J-K^–1-mol^–1. For this type of mixture, it is the first reported case of an M-shaped composition dependence of the excess molar heat capacity at constant pressure.Communicated at the Festsymposium celebrating Dr. Henry V. Kehiaian's 60^th birthday, Clermont-Ferrand, France, 17–18 May 1990.     

Thermodynamic properties of binary mixtures of 2-hexanone withn-alkanes at 35°C

Excess molar enthalpies h ^E and excess molar volumes v ^E of the binary liquid mixtures 2-hexanone+n-alkane (from n-heptane to n-decane) have been determined for various values of the mole fraction of hexanone at 35°C and atmospheric pressure. Excess molar enthalpies were determined by Calvet microcalorimetry and v ^E from densities measured by vibratingtube densimetry. The results are compared with the predictions of several group contribution models.     

Topological and thermodynamic investigations of binary mixtures: Molar excess volumes, molar excess enthalpies and isentropic compressibility changes of mixing

Molar excess volumes, V^E, molar excess enthalpies, H^E, and speeds of sound, u, of o-toluidine (i) + cyclohexane or n-hexane or n-heptane (j) binary mixtures have been determined over entire range of composition at 308.15 K. Speeds of sound data have been utilized to predict isentropic compressibility changes of mixing, of (i + j) mixtures. The observed V^E, H^E and data have been analyzed in terms of Graph theory. The analysis of V^E data by Graph theory reveals that o-toluidine exists as an associated molecular entity and (i + j) mixtures contain 1:1 molecular complex. It has been observed that V^E, H^E and values calculated by Graph theory compare well with their corresponding experimental values. The observed data have also been analyzed in term of Flory theory.     

Topological investigations of the molecular species and molecular interactions that characterize pyrrolidin-2-one + lower alkanol mixtures

Molar excess volumes, V^E, molar excess enthalpies, H^E, and speeds of sound data, u, of pyrrolidin-2-one (i) + ethanol or propan-1-ol or propan-2-ol or butan-1-ol (j) binary mixtures have been determined over entire composition range at 308.15 K. The observed speeds of sound data have been utilized to predict excess isentropic compressibilities, of the investigated binary mixtures. The observed excess thermodynamic properties V^E, H^E and have been analyzed in terms of Graph theory. The analysis of V^E data by the Graph theory suggests that pyrrolidin-2-one exists mainly as a mixture of cyclic and open dimer; ethanol as a mixture of dimer and trimer; butan-1-ol and propan-2-ol as mixture of monomer and dimer and propan-1-ol as a dimer in the pure state, and their mixtures contain 1:1 molecular complex. The IR studies lend additional credence to the nature and extent of interactions for the proposed molecular entities in the mixtures. Also, it has been observed that V^E, H^E and values predicted by the Graph theory compare well to with their corresponding experimental values.     

Thermodynamics of liquid mixtures containing hydrocarbons and strongly polar substances:V E andC P E of {pyridine or piperidine+cyclohexane} at 298.15 K

Summary Excess molar volumesV ^E and excess molar heat capacitiesC _P ^E at constant pressure have been determined, as a function of mole fractionx ₁ at 298.15 K and atmospheric pressure, for the two liquid mixtures {pyridine or piperidine+cyclohexane}. The instruments used were a vibrating-tube densimeter and a Picker flow microcalorimeter, respectively. The two systems show positive excess volumes withV ^E(x ₁=0.5)=0.531 cm³·mol^–1 for {pyridine+cyclohexane} and 0.295 cm³·mol^–1 for {piperidine+cyclohexane}. The curveC _P ^E vs. x ₁ for {pyridine+cyclohexane} shows a rather complex S-shape:C _P ^E is negative at small mole fractionsx ₁ of pyridine and positive forx ₁>0.22, roughly.C _P ^E of the piperidine system is negative throughout and strongly asymmetric with the minimumC _P ^E (x _1,min)=–2.32J·K^–1·mol^–1 being situated at a mole fraction of piperidinex _1,min0.27.

---

Zur Thermodynamik flüssiger Mischungen von Kohlenwasserstoffen und stark polaren Substanzen:V ^E undC _P ^E von {Pyridin oder Piperidin+Cyclohexan} bei 298.15 K

Zusammenfassung Für die beiden flüssigen Mischungen {Pyridin oder Piperidin+Cyclohexan} wurden molare ZusatzvoluminaV ^E und molare ZusatzwärmekapazitätenC _P ^E bei konstantem Druck als Funktion des Molenbruchsx ₁ bei 298.15K bestimmt. Die Messungen wurden mit einem Biegeschwinger-Dichtemeßgerät bzw. einem Strömungsmikrokalorimeter nach Picker durchgeführt. Die Zusatzmolvolumina beider Systeme sind positiv mitV ^E(x ₁=0.5)=0.531 cm³·mol^–1 für {Pyridin+Cyclohexan} und 0.295 cm³·mol^–1 für {Piperidin+Cyclohexan}. Die KurveC _P ^E vs. x ₁ des Systems {Pyridin+Cyclohexan} zeigt einen ungewöhnlichen S-förmigen Verlauf: bei kleinen Molenbrüchenx ₁ von Pyridin istC _P ^E negativ, fürx ₁>0.22 istC _P ^E positiv. Die molare Zusatzwärmekapazität des Piperidinsystems ist überall negativ und stark unsymmetrisch: im Minimum beix _1,min0.27 findet manC _P ^E (x _1,min)=–2.32J·K^–1·mol^–1.

     

Isotopic substitution effects on the volumetric and viscosimetric properties of water-dimethylsulfoxide mixtures at 25°C

Densities and viscosities of binary mixtures (H₂O or D₂O) (1) + (DMSO or DMSO-D6)(2) have been measured over the entire mole fraction range; and the excess volumes, excess viscosities, and excess partial molar volumes Vf of the components have been obtained. All systems show negative excess volume V^e at all compositions, values for mixtures containing D₂O being more negative than those with H₂O byca. 0.03 cm³-mol^-1 at x₁, = 0.6, where a minimum is observed. The difference between DMSO and DMSO-D6 containing mixtures is negligible. The excess viscosity η^e is always positive and shows a maximum at x₁ = 0.65; at this composition, the substitution of H₂O with D₂O causes an excess viscosity increment ofca. 0.35 mPa-s, while deuteration of DMSO brings about a smaller increase,ca. 0.1 mPa-s. The trend of V ₂ ^E with concentration shows the characteristic features of moderately hydrophobic solutes in water (negative values and a minimum in the water-rich region), features that are slightly but significantly more marked in D₂O than in H₂O. The V ₂ ^E values in the water-diluted region and at x₁, =0 are more negative for D₂O than for H₂O.     

Topological and thermodynamic investigations of molecular interactions of aniline and o-toluidine with chloroform

Molar excess volumes, V^E, molar excess enthalpies, H^E, and speeds of sound data, u, of chloroform (i) + aniline or o-toluidine (j) binary mixtures have been measured as a function of composition at 308.15 K. Isentropic compressibility changes of mixing, have been determined by employing speed of sound data. Topological investigations of V^E data reveals that aniline, chloroform and o-toluidine are associated entities and these (i + j) mixtures contain a 1:1 molecular complex. The IR studies lend further support to the nature and extent of interaction for the proposed molecular entity in the mixtures. H^E and values have also been calculated by employing Moelwyn-Huggins concept [Polymer 12 (1971) 387] taking topology of the constituents of the mixtures. It has been observed that calculated H^E and values compare well with their corresponding experimental values. The observed V^E, H^E and data have also been analyzed in terms of Flory theory.     

Volumes of mixing of pyridine bases withn-alkanes: Comparison with the prigogine-flory-patterson theory

The excess molar volumes of binary mixtures pyridine and -picoline + C₆–C₁₀ n-alkanes have been measured at 25°C over the whole composition range. For pyridine + n-hexane and + n-heptane and also -picoline + n-hexane and n-heptane V ^E has an S-shaped behavior and is positive at low concentrations of the base. For the systems pyridine + n-octane + n-nonane + n-decane and -picoline + n-octane, n-nonane, and n-decane V ^E is positive. The Prigogine-Flory-Patterson theory has been fitted to our results.     

Isomer effects in the excess enthalpies of mixtures of alkanes and cycloalkanes

Using the Picker flow calorimeter, excess molar enthalpies H ^E have been obtained at 25°C for mixtures of 1,2-, 1,3- and 1,4-cis- and trans-dimethylcyclohexane and cis- and trans-decalin with n-hexadecane and the highly branched C₁₆ isomer, 2,2,4,4,6,8,8-heptamethylnonane. Values of H ^E are also obtained for cis- and trans-decalin mixed with C₆, C₇, and C₉ isomers. Anomalously low values of H ^E occur for normal alkanes mixed with cycloalkanes in the di-equatorial configuration, suggesting the presence of a negative contribution in H ^E possibly due to a restriction of n-alkane molecular motion by the flat, plate-like cycloalkane.     

Excess Molar Volumes and Excess Partial Molar Volumes of Triethylene Glycol Monoethyl Ether–n-Alcohol Mixtures at 25°C

We have measured excess molar volumes V^E _m of binary mixtures of triethylene glycol monoethyl ether with methanol, ethanol, 1-propanol, 1-pentanol, and 1-hexanol over the full range of compositions at 25°C. The measurements were carried out with a continuous-dilution dilatometer. The excess molar volumes V^E _m are negative over the entire range of composition for the systems triethylene glycol monoethyl ether + methanol, + ethanol, and + 1-propanol and positive for the remaining systems, triethylene glycol monoethyl ether + 1-pentanol, and + 1-hexanol. The excess V^E _m increases in the positive direction with increasing chain length of the n-alcohol. The measured excess volumes have been compared to our previous published data with an effort to assess the effects of replacing methyl by ethyl groups and of inserting oxyethylene groups. The results have been used to estimate the excess partial molar volumes V^E _m,i of the components. The behavior of V^E _m and V^E _m,i with composition and the number of carbon atoms in the alcohol molecule is discussed.     

Excess Molar Volumes and Excess Partial Molar Volumes of Triethylene Glycol Monomethyl Ether–n-Alcohol Mixtures at 25°C

The excess molar volumes V ^E have been measured for binary mixtures of triethylene glycol monomethyl ether with methanol, ethanol, 1-propanol, 1-pentanol, and 1-hexanol as a function of composition using a continuous–dilution dilatometer at 25°C at atmosphere pressure. V ^E are negative over the entire range of composition for the systems triethylene glycol monomethyl ether + methanol, + ethanol, and + 1-propanol, and positive for the remaining systems, containing 1-pentanol and + 1-hexanol. V ^E increases in a positive direction with increasing carbon chain length of the n-alcohol. The excess partial molar volumes V _i ^E of the components were evaluated from the V ^E results. The behavior of V ^E and V _i ^E with composition and the number of carbon atoms in the alcohol molecule is discussed.     

Measurement of Some Thermodynamic and Acoustic Properties of Binary Solutions of N,N-Dimethylformamide with 1-Alkanols at 30°C and Comparison with Theories

Densities, and ultrasonic velocities, uof binary mixtures of N,N-dimethylformamide (DMF) + methanol, + ethanol, + 1-propanol, + 1-butanol, + 1-pentanol, and + 1-hexanol have been measured at 30°C. The ultrasonic velocities have been compared with values calculated from the free-length theory ( FLT) due to Jacobson and collision-factor theory ( CFT) due to Schaaffs. The measured data are used to compute adiabatic compressibility (k _s), deviation in adiabatic compressibility (k _s), intermolecular free length (L _f), molar volume (V _m), and available volume (V _a). The excess molar volume ( V _m ^E) and excess free length (L _f ^E) are also evaluated. For all systems, these results were satisfactorily correlated by the Redlich–Kister polynomial. These parameters are used to discuss dissociation of the self-associated 1-alkanol molecules and the formation of aggregates between unlike molecules through C=O...H–O hydrogen bonding.     

Volumes of mixing 2,4-dimethylpyridine withn-alkanes

In continuation of our work on excess thermodynamic properties of non-electrolyte solutions containing pyridine bases withn-alkanes, we have determined excess molar volumesV ^E for 2,4-dimethylpyridine + C₆ to C₁₀ n-alkanes at 25°C. For the investigated systems noV ^E values were available in the literature for comparison with our data. The experimentalV ^E was used to test the Prigogine-Flory-Patterson theory (PFP), Extended Real Associated Solutions model (ERAS) and the Treszczanowicz-Benson method (TB).     

Excess molar volumes of diethyl carbonate with hydrocarbons or tetrachloromethane at 25°C

The excess molar volumes V _m ^E at atmospheric pressure and at 25°C for binary mixtures of diethyl carbonate with n-heptane, n-decane, n-tetradecane, 2,2,4-trimethylpentane, cyclohexane, benzene, toluene, or tetrachloromethane have been obtained over the whole mole-fraction range from densities measured with a vibrating-tube densimeter. The V _m ^E are positive for all the systems investigated, except for the mixture with toluene which is negative. The results for V _m ^E together with data previously published on excess molar enthalpies H _m ^E and excess molar Gibbs energies G _m ^E , suggest interactions between carbonate and hydrocarbons which are stronger with aromatic than with aliphatic hydrocarbons.Thermodynamics of binary mixtures containing organic carbonates, Part 10.     

Molar excess heat capacities and volumes for mixtures of alkanoates with cyclohexane at 25°C

Molar excess volumes V ^E at 25°C have been determined by vibrating-tube densimetry, as a function of mole fraction x for different series of an alkanoate (H _2m+1 C _m COOC _n H _2n+1 )+cyclohexane. Three types of alkanoates were investigated, i.e., methanoates (m=0, with n=3 and 4), ethanoates (m=1, with n=2, 3, and 4) and propanoates (m=2, with n=1, 2, and 3). In addition, a Picker flow calorimeter was used to obtain molar excess heat capacities C _p ^E at constant pressure at the same temperature. V ^E is positive for all systems and rather symmetric, with V ^E (x=0.5) amounting to almost identical values in a series of mixtures containing an alkanoate isomer of same formula (say C₄H₈O₂, C₅H₁₀O₂, or C₆H₁₂O₂). The composition dependence of C _p ^E is rather unusual in that two more or less marked minima are observed for most of the mixtures, especially when the alkanoate is a methanoate or an ethanoate. These results are discussed in terms of possible changes in conformation of both the ester and cyclohexane.     

Volumes and viscosities of benzene + n-alkane mixtures

Excess molar volumes, viscosities, excess molar viscosities and excess molar activation energies of viscous flow were determined for binary mixtures of benzene + n-hexane, + n-octane, + n-decane, + n-dodecane, + n-tetradecane and + n-hexadecane at 298.15 K. The effect of orientational order of n-alkane on solution molar volumes and viscosities is investigated as well as the adequacy of the absolute rate and free volume theories to predict solution viscosities. For longer n-alkane ΔG*^E and Δ 1n η are positive and associated with the orientational order.     

Molar Excess Volumes and Excess Isentropic Compressibilities of Ternary Mixtures Containing <Emphasis Type="Italic">o</Emphasis>-Toluidine

Molar excess volumes, V _ijk ^E, and speeds of sound, U _ijk , of o-toluidine (i) + benzene (j) + cyclohexane or n-hexane or n-heptane (k) ternary mixtures have been measured as a function of composition at 308.15 K. The observed speed of sound data have been utilized to determine the excess isentropic compressibilities, (K _S ^E) _ijk , of the ternary (i+j+k) mixtures. The Moelywn-Huggins concept (Huggins in Polymer 12: 389–399, 1971) of connectivity between the surfaces of the binary mixture constituents has been extended to ternary mixtures (using the concept of a connectivity parameter of third degree of molecules, ³ ξ, which in turn depends on its topology) to obtain an expression that describes well the measured V _ijk ^E and (K _S ^E) _ijk data. The observed data have also been analyzed in terms of Flory’s theory.     

Thermodynamic and spectroscopic evidence in binary mixtures of nonelectrolytes

Nigam, R.K. and Aggarwal, S., 1986. Thermodynamic and spectroscopic evidence in binary mixtures of nonelectrolytes. Fluid Phase Equilibria, 26: 181–200.Molar excess enthalpies H^E_m of 1,2-dichloroethane (1)+pyridine (2), + α-picoline (2),+n-hexane (2), +n-heptane (2), n-heptane (1)+pyridine (2), +α-picoline (2), +γ-picoline (2), aniline (1)+pyridine 92), +α-picoline (2) and +γ-picoline (2) mixtures have been measured calorimetrically at 298.15 and 308.15 K.The data have been examined in terms of the Lacombe and Sanchez theory and the graph theoretical approach. It was found that these were described better by the graph theoretical approach. The NMR studies on 1,2-dichloroethane (1)+α-picoline (2), aniline (1)+pyridine (2) and aniline (1)+γ-picoline (2) mixtures have also been used to lend credence to the nature and extent of interaction in these mixtures.