Effect of temperature on ionic volumes and heat capacities in methanol

A flow densimeter and flow heat capacity calorimeter have been employed to measure precision densities and specific heats of selected electrolytes and nonelectrolytes in methanol at 20, 25, and 40°C. Apparent molar volumes and heat capacities have been calculated and the corresponding standard state functions, V ^o and C _p, ^o , evaluated. The data have been used, along with known volumes and heat capacity data at 25°C for numerous alkanes, to generate volumes and heat capacities of model compounds for organic electrolytes. Comparison of the thermodynamic functions for the model compounds with those of the corresponding electrolytes at the respective temperatures has made it possible to assign single ion values and to establish the temperature effects of ionic charges on the volumes and heat capacities of solutes.     

Effect of solvent on the partial molal volumes and heat capacities of nonelectrolytes

Group contributions to in seven solvents and to in three solvents have been tabulated. The variation of group parameters is discussed in terms of the solvent compressibility coefficient, _T. The scaled particle theory (SPT) is used to calculate cavity contributions to and C _p2 ^o . Interaction contributions are obtained from the cavity terms and and values estimated through the additivity schemes. values are more sensitive to solute-solvent interactions than in water and less sensitive in methanol. The SPT results for heat capacities support the concept of structural promotion by hydrophobic solutes in water.     

Partial molar heat capacities of selected electrolytes and benzene in methanol and dimethylsulfoxide at 25, 40, and 80°C

A high temperature-high pressure flow heat capacity calorimeter, designed to operate to 350°C and 20 Mpa, has been constructed and tested with aqueous sodium chloride solutions to 80°C. The calorimeter has been used to measure the specific heats for solutions of NaBr, NaClO₄, ₄PBR, NaB₄, and benzene in methanol (MeOH) and dimethylsulfoxide (DMSO) at 40 and 80°C. A commercial calorimeter was used to measure the same systems at 25°C. Apparent molar heat capacities C>_p, have been evaluated and extrapolated to infinite dilution to obtain standard partial molar heat capacities . For electrolytes are positive and insensitive to temperature to 80°C in DMSO, but in MeOH, C _{p, 2} ⁰ for simple electrolytes are negative and become increasingly negative with temperature. The behavior in MeOH is attributed to strong electrostriction by ionic charge and solvation of anions by MeOH molecules which increases with temperature. This is similar to observed behavior of electrolytes in water above 100°C. For benzene is positive in MeOH and DMSO, and increases with temperature.     

Group additivity for the standard partial molal heat capacities and volumes of polar compounds in methanol at 25°C

A flow heat capcity calorimeter and a flow vibrating tube densimeter have been used to measure the apparent molal heat capacities and volumes of benzene and 25 polar compounds in methanol at 25°C. These quantities have been extrapolated to infinite dilution to obtain the standard partial molal heat capacities and volumes. The and data have been used in conjunction with an additivity scheme previously determined for alkanes. Group contributions were evaluatd for –OH, –NH₂, –COOH, –C₆H₅, C=O, –COO–, –CONH–, –O–, –S–, and –S₂–. The concentration dependences of _cp and _v of nonelectrolytes in methanol are qualitatively similar but much smaller than in water.     

Molar Volumes and Heat Capacities of Electrolytes and Ions in Nonaqueous Solvents: 1. Formamide

Apparent molar volumes and heat capacities of 27 electrolytes have been measured as a function of concentration in formamide at 25°C using a series-connected flow densimeter and Picker calorimeter system. These data were extrapolated to infinite dilution using the appropriate Debye–Hückel limiting slopes to give the corresponding standard partial molar quantities. Ionic volumes and heat capacities at infinite dilution were obtained by an appropriate assumption based on the reference electrolyte Ph₄PBPh₄ (TPTB). The ionic volumes, but not the heat capacities, agree reasonably well with previously published statistically based predictions. The values obtained are discussed in terms of simple models of electrolyte solution behavior and a number of interesting features are noted, including, possible dependencies of ionic volumes on solvent isothermal compressibility and of ionic heat capacities on solvent electron acceptor abilities.     

Isentropic compressibilities of univalent electrolytes in methanol at 25°C

A flow densimeter and an ultrasonic sound velocimeter have been used to measure densities and isentropic compressibilities of solutions of LiBr, NaCl, NaBr, Nal, KF, KCl, KBr, Kl, RbBr, Rbl, CsF, CsBr, Ph ₄ PBr, and NaBPh ₄ in anhydrous methanol at 25°C. the latter two electrolytes were also investigated in water at 25°C. Concentrations ranged from about 0.005 m to above 0.25m, solubility permitting. Apparent molar isentropic compressibilities, K_S,, have been calculated and extrapolated to infinite dilution to obtain K _S, ^o . The K _S, ^o values in methanol are all negative, and significantly more negative than the corresponding data in water. Additional data from the literature for acetonitrile and ethanol solutions show that K _S, ^o for the alkali metal halides become more negative in direct proportion to increasing solvent isentropic compressibility. Furthermore, the dependence of K _S, ^o in ionic size also varies in proportion to solvent isentropic compressibility. An explanation of this behavior is presented.     

Partial molar isentropic compressibilities and volumes of selected electrolytes and nonelectrolytes in dimethylsulfoxide

Precision densities and sound velocities for solutions of selected univalent electrolytes and nonelectrolytes in DMSO have been measured at 25°C, and apparent molar isentropic compressibilities and volumes evaluated. The data were extrapolated to infinite dilution to obtain standard state partial molar quantities, K _s,2 ^° , and V ₂ ^° . Values of V ₂ ^° and K _s,2 ^° for alkali metal halides in DMSO are very similar to those in water. The results confirm conclusions derived from data in water and other nonaqueous solvents that K _s,2 ^° and V ₂ ^° for alkali metal halides are strongly dependent on solvent compressibility. K _s,2 ^° becomes more negative and V ₂ ^° decreases as solvent compressibility increases. Attempts to determine ionic K _s,2 ^° values suggest that a significant dissymmetry exists between ₄P⁺ and ₄B^– in DMSO, whereas in water and MeOH, these large ions appear to behave similarly. Ionic V ₂ ^° values support this conclusion. Steric hindrance in the DMSO molecule is believed to be responsible for this dissymmetry.     

Group additivity for partial molal heat capacities and volumes of alkanes in methanol at 25°C

A flow heat capacity calorimeter and a flow vibrating tube densimeter have been used to measure the apparent molal heat capacities and volumes of 14 linear and branched alkanes in methanol at 25°C. These quantities have been extrapolated to infinite dilution to obtain the standard partial molal heat capacities and volumes. The C _p2 ^o and V ₂ ^o data can be expressed by equations having the general form: Y=A_Y+ N_k Y_k+(steric factors), where A_Y is solute independent and the Y_k terms are the individual group contributions. A rationale for use of the above equation is presented.     

Thermodynamics of aqueous phosphate solutions: Apparent molar heat capacities and volumes of the sodium and tetramethylammonium salts at 25°C

A Picker flow microcalorimeter and a flow densimeter were used to obtain apparent molar heat capacities and apparent molar volumes of aqueous solutions of Na₃PO₄ and mixtures of Na₂HPO₄ and NaH₂PO₄. Identical measurements were also made on solutions of tetramethylammonium salts to evaluate the importance of anion-cation interaction. The experimental apparent molar properties were analyzed in terms of a simple extended Debye-Hückel model and the Pitzer ion-interaction model, both with a suitable treatment for the effect of chemical relaxation on heat capacities, to derive the partial molar properties of H₂PO ₄ ^– (aq), HPO ₄ ^2– (aq) and PO ₄ ^3– (aq) at infinite dilution. The volume and heat capacity changes for the second and third ionization of H₃PO₄(aq) have been determined from the experimental data. The importance of ionic complexation with sodium is discussed.     

Apparent molar heat capacities and volumes of electrolytes and ions in acetonitrile-water mixtures

Apparent molar volumes V and heat capacities C_p, of NaCl, KCl, KNO₃, AgNO₃, KI, NaBPh₄ and Ph₄PCl have been measured in acetonitrile (AN)-water mixtures up to x_AN=0.25 by flow densitometry and flow microcalorimetry. Limited data have also been obtained for NaF, LiCl and KBr up to x _AN =0.15. Single ion volumes and heat capacities of transfer were obtained using the assumption _tX(PH₄P⁺) = _tX(BPh₄-) where X=V or C _p and _tX is the change in X for a species on transfer from H₂O to AN-H₂O mixtures. Volumes and heat capacities for simple salts show relatively little dependence on solvent composition. However, _tX for simple ions show more pronounced variations, exhibiting at least one extremum. These extrema are similar to but much less pronounced than those derived previously for ions in t-butanol-water mixtures. Surprisingly little correlation is found between the present data and other thermodynamic transfer functions. This is attributed to the predominance of ion-solvent over solvent-solvent interactions in AN-H₂O solutions. _tV and _tC_p, for the silver ion differ markedly from those of the alkali metal ions as a result of the well-known specific interaction between Ag⁺ and AN.     

Apparent molar heat capacities and volumes of electrolytes and ions int-butanol-water mixtures

The apparent molar volumes V and heat capacities C _p, of NaCl, LiCl, NaF, KI, NaBPh₄ and Ph₄PCl have been determined in solutions of H₂O containing up to 40 mass% t-butyl alcohol (TBA) by flow densitometry and flow microcalorimetry. Combination of these results with literature data allows calculation of V and C _p, for 16 ions in these mixtures using the assumption that _tX(Ph₄P⁺) = _tX(BPh ₄ ^– ) where X=V or C _p and _tX is the change in X for a species on transfer from H₂O to TBA-H₂O mixtures. These are the first reported single ion values for C _p, in a mixed solvent. While whole electrolyte volumes and heat capacities show relatively smooth changes with solvent composition, _tX(ion) exhibit two well-developed extrema at around 10 and 25 mass% TBA. The shape of the _tX(ion) curves shows considerable uniformity among the alkali metal cations and the halide ions but the extrema become more pronounced with increasing size among the tetraalkylammonium ions. These extrema are analogous to those observed in aqueous organic mixtures of surfactants and are probably indicative of microphase transitions in these strongly interacting solvent mixtures.     

Aqueous partial molar heat capacities and volumes for NaTcO4 and NaReO4

A flow microcalorimeter/densimeter system has been commissioned to measure heat capacities and densities of solutions containing radioactive species as a function of temperature. Measurements were made for NaTcO₄(aq) at six temperatures (189.15 K to 373.15 K for the heat capacities, 287.43 K to 396.67 K for the densities) over the molality range 0.01 to 0.29 mol-kg^–1. Measurements for NaReO₄(aq) (NaReO₄ is a common nonradioactive analogue for NaTcO₄) were made under similar conditions, but for eight temperatures and a more extensive range of molalities, 0.05 to 0.65 mol-kg^–1. Heat capacities of NaCl(aq) reference solutions were also measured from 293.15 K to 398.15 K.The heat capacity and density data are analysed using Pitzer's ioninteraction model. Equations for the apparent molar heat capacities and volumes are reported. Values of the NaReO₄(aq) partial molar heat capacities are compared to literature values based on integral heats of solution. The agreement between the two sets of NaReO₄ results is good below 330 K, but only fair at the higher temperatures. Values of the partial molar volumes have also been derived. Using literature values and the results of our experiments, it is calculated that the disproportionation of hydrated TcO₂(s) to form TcO ₄ ^– (aq) and Tc(cr) occurs more readily at high temperatures. The uncertainties introduced by using thermodynamic values for ReO ₄ ^– (aq), in the absence of values for TcO ₄ ^– (aq), are discussed.     

Single ionic partial molar volumes and solvation of ions

The limiting partial molar volumes of alkali metal halides in water and some other protic solvents have been dissected into individual ionic contributions. The extra-thermodynamic procedure employed assumes independent contributions of ion-solvent and solvent-solvent interactions to this property. The resulting parameters are found to be chemically reasonable and consistent with the molecular properties of the solvents. The limiting partial molar volume of the hydrogen ion has been calculated to be –4.2 cm³-mol^–1 in water at 25°C. Analysis of data for aqueous solutions from 0 to 50°C permits the evaluation of the energy change associated with the transfer of a water molecule from the bulk to the hydration zone. Results from the present work are compared with those obtained from the scaled particle theory.     

Thermodynamics of aqueous EDTA systems: Apparent and partial molar heat capacities and volumes of aqueous strontium and barium EDTA

Apparent molar heat capacities and volumes have been determined for Na₂SrEDTA (aq) and Na₂BaEDTA (aq). Standard state partial molar heat capacities and volumes have been calculated as well as the partial molar properties at 0.1 m ionic strength that are needed for various thermodynamic calculations. Selected enthalpies and stability constants from the literature have been combined with out heat capacities to generate predicted stability constants to 200°C.     

Apparent molar volumes and heat capacities of aqueous solutions of sodium benzenesulfonate at 25°C

Apparent molar volumes and heat capacities of sodium benzenesulfonate have been measured at 25°C and at molalities up to 1.1 molal using a Picker flow densimeter and a Picker flow heat capacity calorimeter. Data for both properties have been modeled with Pitzer equations for the respective functions, and the standard state values evaluated. The apparent molar volume of sodium benzenesulfonate appears to be relatively insensitive to sample preparation. Possible reasons for the difference in the apparent molar volume reported here and the literature value are discussed.     

Thermodynamic properties of peptide solutions 3. Partial molar volumes and partial molar heat capacities of some tripeptides in aqueous solution

Partial molar volumes, V ₂ ^o , and partial molar heat capacities, C _p,2 ^o , of the tripeptides glycylglycylglycine, glycylglycylalanine, glycylalanylglycine and alanylglycylglycine have been determined in aqueous solution at 25°C. For the three alanyl-containing tripeptides, the data indicate that the tripeptide-water interaction is influenced by the side chain position within the molecule. The results have been rationalized in terms of likely solutesolvent interactions. The V ₂ ^o and C _p.2 ^o data have also been used to calculate the contribution to these properties of a-CH₃ side chain.     

Thermodynamic properties of the ethylammonium nitrate + water system: Partial molar volumes,heat capacities,and expansivities

Partial molar volumes at 15, 25, and 45°C and partial molar heat capacities and expansivities at 25°C for ethylammonium nitrate + water mixtures are reported. The results are compared with those for other aqueous cosolvents, particularly hydrazine and ammonium nitrate.     

Apparent molar volumes, expansibilities, and isentropic compressibilities of selected electrolytes in methanol

Densities of solutions of sodium bromide, sodium perchlorate, sodium tetraphenylborate, and tetraphenylphosphonium bromide in methanol at the temperatures ranging from 283.15 to 313.15 K have been measured. Ultrasound velocities for the above systems at T = 298.15 K have been determined. From the obtained data, the partial molar volumes and the partial molar isentropic compressibilities for electrolytes in solution have been estimated. Division into the ionic contributions has been proposed on the basis of the reference electrolyte method. The existence of the high-volume intermediate shell with an enhanced structure has been suggested.     

Heat capacities and volumes of NaI in mixtures of dimethylformamide and several non-electrolytes

Heat capacities and densities of solutions of NaI in mixtures of N,N-dimethylformanide (DMF) with isobutanol, formamide, acetone, tetrahydrofuran, ethylene glycol, 2-methoxyethanol, n-propanol and benzo-15-crown-5-ether have been measured at 25°C. The apparent molar volumes of NaI in mixtures of DMF with isobutanol, formamide, ethylene glycol, n-propanol, and 2-methoxyethanol increase with the amount of these non-electrolytes, while in the systems containing acetone, tetrahydrofuran and benzo-15-crown-5 ether a decrease is observed. The apparent molar heat capacity of NaI in the system containing the crown ether is higher than that in pure DMF. In all other cases C_p, of NaI decreases with the amount of non-electrolyte. Finally, the non-ideal contributions to heat capacity and volume as a result of the interaction between pairs of unlike solutes, respectively c_XY and v_XY with X=NaI and Y=non-electrolyte, are calculated.On leave from the University of Lódz, Department of Physical Chemistry, ul. Nowotki 18, 91-416 Lódz, Poland.     

Apparent molar heat capacities and volumes,van der Waals volumes and accessible surface areas of alkylated derivatives of cytosine and uracil in aqueous solutions at 25°C.

Densities and specific heat capacities of aqueous solutions: 1,3,5,6-tetramethyluracil, 1,6-dimethyl-3-ethyluracil, 1,6-dimethyl-3-propyluracil, 1,6-dimethyl-3-butyluracil, 1,N⁴-trimethylcytosine, 1,N⁴-dimethyl-5-ethylcytosine, 1,N⁴ dimethyl-5-propylcytosine, 1,N⁴-dimethyl-5-butylcytosine were determined using flow calorimetry and flow densimetry at 25°C. Apparent molar volumes and heat capacities, van der Waals volumes and accessible surface areas were determined. It was stated that for alkylcytosines and alkyluracils partial molar volumes and heat capacities correlate linearly with the number of substituted methylene groups-CH₂-as well as with the van der Waals volumes and accessible surface areas of the compounds studied; for cyclooligouracils the cyclization effect was discussed.