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1.
Supercooling temperatures and enthalpies of mixing with some solvents have been examined for two kinds of solutions subjected to different thermal treatments (solutions I and II) of tetrahydrofuran (THF), isopropyl alcohol (2-PrOH), and ethyleneglycol butylether (BE), and ethyleneglycol isobutylether (i-BE) in order to observe more directly the structural organization of water molecules around a nonpolar molecule in an aqueous solution. For THF and 2-PrOH solutions, supercooling temperatures of solution I were found to be 2–3 degrees higher than those of solution II, and differences HI-HII were found to be about 3 kJ mol–1. It has been concluded that these results directly reflect the difference in the stability of hydrogen-bonded water networks in an aqueous solution.  相似文献   

2.
The enthalpies of dilution of aqueous solutions of methanol, ethanol, l-propanol, 2-propanol, 1-butanol, l-pentanol, 1-hexanol, cyclohexanol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol and poly-alcohol(cyclohexaamylose) have been determined at high dilution as a function of the mole fraction of alcohol at 298.15 K, by a rocking twin-microcalorimeter of the heat-conduction type. A smoothing equation of the enthalpies of dilution against the mole fractions of alcohols are given. The graphical comparison of experimental results with their smoothed values or literature ones, taking into account the dependence of the mole fractions, are also presented. It has been found for the aqueous solutions of shorter n-alcohols than hexanol that at very high dilution, exothermic values of molar enthalpies of dilution from a definite mole fraction of alcohols to infinite dilution with the change of mole fraction is proportional to carbon number of n-alcohols. The molar enthalpies of infinite dilution of aqueous butanediol isomers and 1-hexanol were very large. Molar enthalpies of infinite dilution of aqueous poly-alcohol (cyclohexaamylose) were endothermic. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

3.
Ultrasonic speeds in, and isentropic compressibilities of, aqueous solutions of water + 2-butoxyethanol (2BE)+t-butanol have been determined at 298.15 K. The concentrations of t-butanol at which the ultrasonic speed becomes maximum and isentropic compressibility becomes minimum are found to decrease with increases in the concentration of 2BE, x 2BE, in the cosolvent (aqueous 2BE). This behavior indicates that the aqueous ternary solutions are less structured than aqueous t-butanol. In the presence of 2-butoxyethanol, enhancement in the hydrogen bonded structure of water due to hydrophobic hydration between t-butanol and water molecules decreases as the concentration of x 2BE in the cosolvent increases. When x 2BE>0.2, the ternary solution behaves like a normal liquid. This behavior is also very well reflected in the concentration dependence of the excess ultrasonic speed and excess isentropic compressibility. The optimum concentrations of t-butanol, ($x_{\mathrm{t}\mbox{-}\mathrm{B}}$x_{\mathrm{t}\mbox{-}\mathrm{B}})opt, at which extrema in ultrasonic speed, isentropic compressibility, excess ultrasonic speed and excess isentropic compressibility are observed decrease with increase in x 2BE in the cosolvent. The results are explained as being due to a reduction in the strength of hydrophobic interactions responsible for enhancement in the structure of water in aqueous t-butanol in the presence 2BE. Beyond (xt-Bx_{\mathrm{t}\mbox{-}\mathrm{B}})opt, the hydrogen bonded network of water collapses and water, 2-butoxyethanol and t-butanol molecules interact with each other as normal liquid molecules.  相似文献   

4.
We have been evaluating third derivative quantities of the Gibbs free energy, G, by graphically differentiating the second derivatives that are accessible experimentally, and demonstrated their power in elucidating the mixing schemes in aqueous solutions. Here we determine directly one of the third derivatives of G, the partial molar entropy-volume cross fluctuation density of 2-butoxyethanol (BE) in the BE–H2O system, SV δ BE . The difference of the heats of compression were directly determined using two identical cells and applying the same pressure change to both cells concurrently. Both cells are filled with sample solutions having a small appropriate difference in mole fraction. The results indicated that this method is feasible with the prior knowledge of the thermal expansivity of the solution to within a few per cent accuracy. If the volumes of the two cells are identical within the order of 0.01%, the method provides the required results to within 0.1% without the thermal expansivity data. This success opens a possibility of evaluating the fourth derivative graphically, which is expected to provide much more detailed information about the molecular processes in aqueous solutions.  相似文献   

5.
The mixing enthalpies of aqueous heavy rare alkali metal chloride RbC1 solutions with aqueous α-amino acid (Loglycine, L-alanine and α-aminobutyric acid) solutions, as well as the dilution enthalpies of RbC1 and α-amino acid solutions in pure water had been measured at 298.15K. The transfer enthalpies of RbCI from pure water to aqueous α-amino acid solutions could be obtained from these data. The enthalpic pair interaction parameters of RbC1 with α-amino acid in water have been evaluated according to the McMillan-Mayer theory and discussed in terms of the electrostatic interaction, structure interaction and Savage-wood group additivity mode.  相似文献   

6.
The concentration effect on the dilution enthalpies (Δdil H m) of colchicine (COL) in aqueous NaCl solutions has been investigated by isothermal titration microcalorimetry at 298.15 K. The corresponding homogeneous enthalpic interaction coefficients have been calculated according to the excess enthalpy concept. The results show that the dilution enthalpies of COL in aqueous NaCl solutions at different mass fractions are positive. The overall trend is that enthalpies of dilution become more positive with the increase of the salt mass fraction. The values of enthalpic pair-wise interaction coefficients, h 2, have been obtained by fitting the data of the enthalpies of dilution with a viral expansion. The results can be interpreted from the view of solute-solute and solute-solvent interactions involved in the solvent effects.  相似文献   

7.
The enthalpies of mixing of six kinds of amino acid (glycine, L-alanine, L-valine, L-serine, L-threonine, and L-proline) with glycerol in aqueous solutions and the enthalpies of diluting of amino acid and glycerol aqueous solutions have been determined by flow microcalorimetry at 298.15 K. Employing McMillan–Mayer theory, the enthalpies of mixing and diluting have been used to calculate heterogeneous enthalpic pairwise interaction coefficients (h xy ) between amino acids and glycerol in aqueous solutions. Combining h xy values of amino acids with glycol in the previous study, the variations of the h xy values between amino acids and glycerol have been interpreted from the point of view of solute–solute interactions.  相似文献   

8.
The enthalpies of mixing of aqueous hydrofluoric and hydrochloric acids and the enthalpies of dilution of the ternary solutions HF/HCl/H2O at fixed concentration of HCl have been measured. The standard enthalpies of formation of HF in these solutions have been derived.  相似文献   

9.
The heats of mixing of aqueous solutions of copper(II) or nickel(II) nitrate in water + acetamide (AA) mixtures in the existing range of amide concentrations have been studied. A rise in the amide concentration enhances solvation more strongly in copper(II) salt solutions. Data are analyzed with reference to previous results on the enthalpies of transfer of the salts studied in water + formamide (FA) and water + N,N-dimethylformamide (DMF) mixtures. Electronic absorbance spectra have been recorded at a fixed electrolyte concentration for all thermochemically studied systems, and a linear correlation has been found between the enthalpy of transfer of Cu(NO3)2 and the optical density of the solution. The enhanced solvation of copper(II) nitrate in aqueous acetamide is due to inner-sphere interactions between the cation and acetamide; that of nickel(II) nitrate is more due to outer-sphere interactions.  相似文献   

10.
Enthalpies of mixing of ethanol solution of R- and S-enantiomers of limonene in large concentration have been measured at 298.15 K. The enthalpies of mixing were negligibly small for all concentrations. Enthalpies of mixing showed negative in less than 30 mol%, but positive in more than the high concentration of limonenes. The heterochiral solutions were more stable than each of the homochiral solutions in dilute solutions. The concentration dependence on enthalpies of mixing in dilute concentration of less than 10 mol% was much sharper in inclination than the dense solutions limonene.  相似文献   

11.
The heats of mixing ofn-butyl amine with methanol andn-propanol have been determined at 30° C and the enthalpies of alcohol-amine complex formation have been calculated by thermochemical cycle. The enthalpies of complex formation of butyl amine with methanol andn-propanol were found to be-44.3 kJ/mole and-39.4 kj/mole respectively. The heats of mixing of synthetically prepared 1:1 molar mixtures of n-butyl amine with methanol, ethanol andn-propanol withn-hexane have also been determined at 30° C. The enthalpy of amine-alcohol complexes was obtained from the partial molar heats of dissociation of the complexes inn-hexane. The values agree with those obtained by the thermochemical cycle method. NCL Communication No. 2561.  相似文献   

12.
The enthalpies of mixing aqueous ethanol solutions and with aqueous amino acid solutions (glycine, L-alanine, L-serine, L-threonine, and L-proline) and their respective enthalpies of dilution have been determined at 25°C by a flow microcalorimetric system. The experimental data have been analyzed in terms of McMillan-Mayer formalism to obtain the enthalpic virial coefficients for heterotactic interaction. The results have been interpreted from the point of view of solute-solute interactions.  相似文献   

13.
Excess chemical potentials and excess partial molar enthalpies of 1,2- and 1,3-propanediols (abbreviated as 12P and 13P), E i, and H E i (i = 12P or 13P) were determined in the respective binary aqueous solutions at 25°C. For both systems, the values of E i are almost zero, within ±0.4 kJ-mol–1. However, the excess partial molar enthalpies, H E i show a sharp mole fraction dependence in the water-rich region. Thus, the systems are highly nonideal, in spite of almost zero E i. Namely, the enthalpy-entropy compensation is almost complete. From the slopes of the H E i against the respective mole fraction x i we obtain the enthalpic interaction functions between solutes, H i–i E, (i = 12P or 13P). Using these quantities and comparing them with the equivalent quantities for binary aqueous solutions of 1-propanol (1P), 2-propanol (2P), glycerol (Gly), and dimethyl sulfoxide (DMSO), we conclude that there are three composition regions in each of which mixing schemes are qualitatively different. Mixing Schemes II and III, operative in the intermediate and the solute-rich regions, seem similar in all the binary aqueous solutions mentioned above. Mixing Scheme I in the water-rich region is different from solute to solute. 12P shows a behavior similar to that of DMSO, which is somewhat different from typical hydrophobic solute, 1P or 2P. 13P, on the other hand, is less hydrophobic than 12P, and shows a behavior closer to glycerol, which shows hydrophilic behavior.  相似文献   

14.
The enthalpies of transfer 2-propanol, 1,2-butanediol (BD) and 1-hexanol from aqueous to aqueous α-cyclodextrin (CD) solutions have been determined by microcalorimetry at various mole fractions at 298.15 K. To clarify stabilities of inclusion complexes in aqueous solutions, hydration Gibbs energies calculation of inclusion complex of CD-alcohol were performed by using the molecular mechanics with the MMFF94s force field in the generalized born/surface area (GB/SA) model. The largest stabilization in Gibbs energy is obtained by the hydration (Δhyd H) of α-CD-1,2-butanediol complex among α-CD-butanediol isomers complexes.  相似文献   

15.
The enthalpies of solution of urea (U) in water (W)-tert-butanol (TBA) mixtures and of TBA in W-U mixtures, the enthalpies of dilution of TBA in W, and the enthalpies of mixing of U and TBA aqueous solutions were measured with a solution calorimeter and a flow microcalorimeter. Enthalpies of transfer of U and TBA to the mixed solvents were derived. Also, pair and triplet interaction parameters between the various solutes were derived from the mixing and dilution experiments. The enthalpic pair parameter hU-TBA is positive, suggesting that the main contribution to this parameter is the decrease in hydrophobic hydration of TBA in the presence of U.  相似文献   

16.
The enthalpies of mixing of L-arginine with 2,2,2-trifluoroethanol and their respective enthalpies of dilution in aqueous solutions at 298.15, 303.15 and 310.15 K were determined as a function of the mole fraction by flow microcalorimetric measurement. These experimental results were analyzed to obtain heterotactic enthalpic interaction coefficients(hxy, hxxy, hxyy) according to the McMillan-Mayer theory. The hxy coefficients between L-arginine molecule studied and 2,2,2-trifluoroethanol molecule in aqueous...  相似文献   

17.
The enthalpies of mixing of aqueous solutions have been determined for sucrose with six different amino acids (glycine, l-alanine, l-serine, l-valine, l-proline and l-threonine) at 298.15 K, by using a LKB-2277 flow microcalorimetric system. These results, along with the enthalpies of dilution of these solutes for the initial solutions, were used to determine the enthalpic interaction coefficients (h xy, h xyy, h xxy) of the McMillan–Mayer Theory. The pair-wise cross interaction coefficients of amino acids and sucrose are discussed from the viewpoint of solute–solute interactions.  相似文献   

18.
Calorimetric measurements have been made of the differential enthalpies of solution as a function of composition of both components in the binary systems tetraethyleneglycol octylether (C8E4)-water and polyethyleneglycol 400 (PEG)-water, as a function of composition, at three different temperatures. Heat capacity changes for dissolution were calculated from the temperature variation of the solution enthalpies. Excess enthalpies and excess heat capacities of mixing were calculated from the differential enthalpies of solution. All measurements on C8E4 were made above the critical micelle concentration (c.m.c.) so the results relate to C8E4 in aggregated form. The thermochemical properties of the C8E4 and PEG systems with water are similar. The differential solution enthalpy of the organic solute in pure water is fairly exothermic and then increases smoothly with increasing solute content. Likewise the solution enthalpy of water in pure C8E4 or PEG is fairly exothermic, but increases steadily to become zero at a water content corresponding to more than five water molecules per ethyleneoxide group. The measurements on the C8E4 system at 40°C were made close to the demixing temperature. The results are compared with previously reported results on the 2-butoxyethanol (BE)-water system.  相似文献   

19.
The effect of ascorbic acid and its analogue 5,6-O-isopropylidenyl-2,3-O-dimethylascorbic acid (I), which has been synthesized for the purpose and does not contain mobile hydrogen atoms, on the formation of the products of continuous radiolysis of deaerated ethanol and its aqueous solutions has been studied. The ionization potentials, the molecular orbital energies, the enthalpies of homolytic dissociation of C-H and O-H bonds, and the enthalpies of H atom addition to the C=O group of the test compounds have been calculated by ab initio methods. The array of the experimental and calculated theoretical data suggests that both ascorbic acid in the undissociated form and compound I can oxidize α-hydroxyethyl radicals, whereas the monoanion of ascorbic acid acts as a reducing agent in the reactions with these transient radicals. The reduction of α-hydroxyethyl radicals in aqueous solutions by the ascorbic acid monoanion can follow both the hydrogen transfer and electron transfer mechanisms.  相似文献   

20.
Enthalpies of dilution of aqueous L-serine, pyridine and methylpyridine solutions and their enthalpies of mixing have been determined by a mixing-flow microcalorimeter at 298.15 K. The data have been analyzed in terms of McMillan-Mayer formalism to fit to virial polynomials from which the heterotactic enthalpic pairwise interaction coefficients, h xy, betweenL-serine and pyridine and methylpyridine isomers have been evaluated. The results obtained in the present paper are compared with those reported in the earlier paper about glycine and L-alanine in the same organic solvent aqueous solutions, giving a global insight of the interaction mechanism between the a-amino acids and pyridine and methylpyridine from the point of view of solute-solute interactions and substituent effects of methyl groups introduced into the pyridine ring. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

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