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  • 1
    Electronic Resource
    Electronic Resource
    Viscosities of solutions of electrolytes and non-electrolytes in ethylene carbonate at 40°C (1982)
    Springer
    Journal of solution chemistry 11 (1982), S. 1-15 
    Details
    ISSN: 1572-8927
    Keywords: Ethylene carbonate ; viscosity ; Jones-Dole equation ; nonaqueous solvent ; solvation ; tetraalkylammonium ions ; alkali metal halides ; electrolytes ; non-electrolytes ; partial molal volumes ; high dielectric constant solvents
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The viscosities of dilute solutions of a number of tetraalkylammonium and alkali metal halides, tetraphenylarsonium chloride, sodium tetraphenylborate, tetrabutylammonium tetrabutylborate, water, and 3,3-diethylpentane have been measured in the high-dielectric constant solvent, ethylene carbonate (EC) at 40°C. Crude values of the apparent molar volumes of these solutes have also been obtained. Relative viscosities were fitted to the extended Jones-Dole equation, ηr=17#x002B;A η c 1/2+B η C+D η c 2.The pattern of the Bη coefficients is strikingly similar to that previously observed in the high dielectric constant, linear-chain hydrogen-bonded solvent, N-methylacetamide (NMA). Ionic values for φv and Bη have been obtained using a variety of splitting techniques. Alkali metal ions have large Bη coefficients indicating strong cation solvation with the ‘normal’ order Li〉Na〉K〉Cs. Small anions have positive but much smaller Bη values than in NMA. The observed order does suggest, however, a small degree of anion solvation. Large organic ions do not display the sharp crossing of the Einstein law,D η=2.5φv, uniquely characteristic in H2O of hydrophobic interaction. The two non-electrolytes have negative Bη coefficients showing that the Einstein law is not valid at the molecular level and that hydrocarbons are not good models for their isoelectronic tetraalkylammonium ion counterparts. An empirical modification of the Einstein law to account for the finite size of the solvent molecules is discussed. As in NMA the Dη coefficients are roughly linear in the square of Bη suggesting that they arise from hydrodynamic origins.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00664330
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  • 2
    Electronic Resource
    Electronic Resource
    Absolute calibration of flow calorimeters used for measuring differences in heat capacities. A chemical standard for temperatures between 325 and 600K (1982)
    Springer
    Journal of solution chemistry 11 (1982), S. 223-236 
    Details
    ISSN: 1572-8927
    Keywords: Heat capacity ; standard, Picker calorimeter ; calibration ; aqueous sodium chloride ; heat loss ; flow calorimeter
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Two methods for the absolute calibration of flow calorimeters (used for measuring the differences in heat capacities of two fluids) have been investigated. In the recommended method of calibration, a change in the flow rate of the fluids is used to minic a change in the heat capacity of the fluid. In the other method of calibration, heat loss is measured using a fluid of known heat capacity, and it is assumed this heat loss is constant. This calibration method is not recommended because the heat loss is, in general, not constant. For some calorimeters the difference between the two methods of calibration is negligible, while for others erros as high as 40% are caused by choosing the wrong method. A detailed analysis of the heat losses in this kind of calorimetry shows why the two calibration methods give different results and leads to various methods of improving calorimeter construction and operation. Because chemical standardization is far more convenient for routine use, the recommended absolute calibration method has been used to establish 3.00 mol-kg−1 aqueous NaCl as a chemical standard for temperatures between 325 and 600K at 17.7 MPa.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00657315
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  • 3
    Electronic Resource
    Electronic Resource
    Enthalpies of dilution of aqueous solutions of amides and alcohols (1982)
    Springer
    Journal of solution chemistry 11 (1982), S. 295-308 
    Details
    ISSN: 1572-8927
    Keywords: Enthalpies ; dilution ; aqueous ; amides ; alcohols ; formamide ; dimethylformamide ; inositol ; cyclohexanol ; mannitol
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Enthalpies of dilution of aqueous systems containing formamide, dimethyl-formamide, the mixture of these amides, and each amide separately with mannitol, inositol, and cyclohexanol have been determined at 25°C. The data have been treated in terms of the Savage-Wood additivity principle and in combination with literature data. New values for the methylene-amide, carbinol-amide, and amide-amide group interaction enthalpies are presented. These may be used with data on a wider variety of solute systems to obtain interaction enthalpies for new groups.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00649288
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  • 4
    Electronic Resource
    Electronic Resource
    Enthalpy of dilution of aqueous systems containing S-trioxane and some amides. Analysis of the interaction of saccharides with amides in aqueous media (1982)
    Springer
    Journal of solution chemistry 11 (1982), S. 481-493 
    Details
    ISSN: 1572-8927
    Keywords: Enthalpy ; dilution ; S-trioxane ; amides ; aqueous ; interactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Enthalpies of dilution of aqueous systems of trioxane+formamide and trioxane+dimethylformamide have been determined at 25°C. The data have been treated in terms of the Savage-Wood additivity principle, and a first estimate of the pairwise group interaction enthalpy for-O-/CONH is presented. Systems of saccharides and amides are not amenable to the Savage-Wood treatment used in recent works. However, when treated in conjunction with all available data to yield a different set of group interaction parameters, saccharides behave more predictably. Implications of this state of affairs are considered.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00647110
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  • 5
    Electronic Resource
    Electronic Resource
    Interactions in aqueous nonelectrolyte systems. Gibbs energy of interaction of the ether group with the hydroxyl group and the amide group (1985)
    Springer
    Journal of solution chemistry 14 (1985), S. 781-794 
    Details
    ISSN: 1572-8927
    Keywords: Freezing points ; aqueous solutions ; group interactions ; trioxane ; dioxane ; inositol ; mannitol ; cyclohexanol, formamide, and acetamide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Freezing temperatures of dilute aqueous solutions of equimolar mixtures of 1,3,5-trioxane with myo-inositol, d-mannitol, cyclohexanol, formamide, and acetamide, and 1,4-dioxane with myo-inositol, d-mannitol, formamide, and acetamide have been measured. These data yield pairwise Gibbs energies of interactions between the molecules in an aqueous solution. Using the group additivity principle, the results also yield the pairwise functional group Gibbs energies of interaction for the ether group with the hydroxyl and amide group. These results have been combined with all available data from the literature to yield the Gibbs energy and enthalpy of interaction of amides, ethers, alcohols, and saccharides in aqueous solution.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00646000
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  • 6
    Electronic Resource
    Electronic Resource
    Freezing temperatures and enthalpies of dilution of aqueous solutions of amides. Gibbs energies and enthalpies of interaction of the N,N-dimethylamide group in aqueous solutions (1985)
    Springer
    Journal of solution chemistry 14 (1985), S. 393-405 
    Details
    ISSN: 1572-8927
    Keywords: Enthalpies ; dilutions ; aqueous ; amides ; freezing points ; group interactions ; densities ; additivity principles
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Enthalpies of dilution, freezing temperatures, and densities of aqueous solutions of N,N-dimethylacetamide and N,N-dimethylpropionamide have been measured. Freezing temperatures of dilute aqueous solutions of formamide and N,N-dimethylformamide have also been measured. These data yield the pairwise molecular Gibbs energies and enthalpies of interaction: these have been treated according to a group additivity principle to give pairwise functional group Gibbs energies and enthalpies of interaction. The results indicate that substitution on the amide nitrogen may increase the Gibbs energy and enthalpy of interaction of the amide group with itself in an aqueous environment but the effect if present is small.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00643943
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  • 7
    Electronic Resource
    Electronic Resource
    Equilibrium constant for the catenation of two hard tori (1993)
    Springer
    Journal of solution chemistry 22 (1993), S. 299-309 
    Details
    ISSN: 1572-8927
    Keywords: Torus ; catenation ; catenate ; metal complex
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The equilibrium constant and Gibbs energy for the catenation reaction of two hard tori were calculated at several values of the ratio of minor radius to major radius γ-r t /R t . The results were used to 1) estimate the fraction of catenated molecules formed in a ‘statistical’ synthesis, and 2) estimate the theoretical maximum increase in complexing ability obtained by catenation of two complexing ligands. The catenated complexing ligands synthesized by Dietrich-Buchecker et al. do not realize the theoretical enhancement due to confinement of the ring motions in the metal complex. Theoretical arguments show that, in the case of ideal gas and colligative properties, the catenated molecule must be considered as one molecule even though it is only held together by topological bonds.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00647202
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  • 8
    Electronic Resource
    Electronic Resource
    Freezing points, osmotic coefficients, and activity coefficients of some salts in ethylene carbonate: A high dielectric constant solvent without hydrogen bonding (1978)
    Springer
    Journal of solution chemistry 7 (1978), S. 799-812 
    Details
    ISSN: 1572-8927
    Keywords: Freezing points ; conductances ; densities ; alkali halides ; tetraalkylammonium halides ; ethylene carbonate ; osmotic coefficients ; activity coefficients ; aprotic solvent
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The freezing points, conductivities, and densities of NaI, KI, CsI, Bu4NCl, Bu4NBr, Bu4NI, Et4NBr, and Pr4NBr (where Et = ethyl, Pr = propyl, and Bu =n-butyl) in ethylene carbonate have been measured. Osmotic and activity coefficients were calculated from the results. All of the salts studied are strong electrolytes. The trends in the osmotic coefficients of the alkali metal iodides are NaI〉KI〉CsI, showing that Na+ is more solvated by ethylene carbonate than Cs+. For the tetraalkylammonium halides, the order of osmotic coefficients are Et4NBr≃Pr4NBr≃Bu4NCl〉Bu4NBr〉Bu4NI. This is the same order as observed in two other high-dielectric-constant solvents, water andN-methylacetamide. The results indicate that the smaller anions are more solvated than the larger anions in ethylene carbonate in contrast to the usual behavior of dipolar aprotic (basic) solvents, such as dimethyl sulfoxide.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00650809
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  • 9
    Electronic Resource
    Electronic Resource
    Salting-in of alcohols in aqueous solutions by tetraalkylammonium bromides at the freezing temperature (1978)
    Springer
    Journal of solution chemistry 7 (1978), S. 165-178 
    Details
    ISSN: 1572-8927
    Keywords: Salting-in ; freezing-point depression ; alcohols ; tetraalkyl-ammonium bromides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The freezing-point depression of the ternary systems tetraalkylammonium bromides-t-butanol-water for the first five homologs of R4NBr was measured. In the case of Bu4NBr, the effect of size of the alcohol (methahol ton-butanol) was also investigated. From the corresponding freezing-point data for the binary systems the apparent salting constants were calculated. The true salting constantsk s were obtained by extrapolation to infinite dilution. These are all very close to zero at the freezing temperature. From the corresponding thermochemical data the temperature dependence ofk s was calculated, and above 5°C all the R4NBr salts int-butanol; the salting-in increases with temperature and with the size of the hydrophobic cations. The scaled-particle theory is at present the only one which can account semiquantitatively for the temperature dependence of the salting-in effect.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00650524
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  • 10
    Electronic Resource
    Electronic Resource
    Enthalpies of dilution of aqueous systems containing hexamethylenetetramine and other nonelectrolytes (1982)
    Springer
    Journal of solution chemistry 11 (1982), S. 729-747 
    Details
    ISSN: 1572-8927
    Keywords: Enthalpy of dilution ; aqueous solutions ; group interaction enthalpies ; Savage-Wood principle ; cyclohexanol ; formamide ; hexamethylenetetramine ; mannitol ; myoinositol ; dimethylformamide ; trioxane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Enthalpies of dilution of aqueous systems containing hexamethylenetetramine, alone and in ternary system with each of mannitol, myoinositol, cyclohexanol, formamide, dimethylformamide, and trioxane have been determined. The data have been treated in terms of the Savage-Wood additivity principle and first estimates for the pairwise groups interaction enthalpies of N/N, CH2/N, CHOH/N, COHN/N and −O−/N have been made. The results are discussed in light of all other known group interaction enthalpies. The limitations and utilities of the Savage-Wood principle are reviewed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00645339
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