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  • 1985-1989  (419)
  • 1
    ISSN: 1572-8927
    Keywords: AgCl ; solubility ; complexes ; stability constants ; heats
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Available data on the solubility of silver chloride in aqueous solutions of HCl, NaCl, KCl, LiCl, and NH4Cl, along with potentiometric measurements of the activity of Ag+ in aqueous NaCl−NaClO4 mixtures, have been analyzed to obtain the thermodynamic properties of the (AgCl)0, AgCl 2 − , AgCl 3 2− , and AgCl 4 3− complexes. Results obtained include the stability constants of the complexes and 25°C, the virial parameters needed to calculate the activity coefficients of the complexes and the heats of the reactions by which they are formed. These results are sued to calculate tables of recommended values for the solubility of silver chloride in the host solutions as a function of concentration from 0 to 150°C and to make a critical evaluation of the reliability of previously published data.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-8927
    Keywords: Sea salts ; NaCl ; Na2SO4 ; MgSO4 ; MgCl2 ; volumes of mixing ; densities
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The densities of mixtures of the six possible combinatons of the major sea salts (NaCl, Na2SO4, MgSO4, and MgCl2) were determined at constant ionic strengths of I=1.0 and I=3.0 at 25°C. The results are used to determine the volume changes for mixing (ΔV m ) the major sea salts. The values of ΔV m were fit to equations of the form ΔV m where y i is the molal ionic strength fraction of solute i, and υ0 and υ1 are parameters related to the interaction of like-charged ions. The cross-square rule was found to hold at both ionic strengths. Density estimates were made without and with the addition of volume of mixing terms to Young's Rule and compared to the experimental values. The densities calculated with the addition of volume of mixing terms gave better estimates, demonstrating that the densities of concentrated brines can be more accurately estimated using ΔV m terms. The equations of Reilly and Wood which include the cross-square rule were used to estimate the densities of the cross mixtures (NaCl−MgSO4 and MgCl2−Na2SO4). The estimated densities agree with the measured values to within ±30 ppm at I=1.0 and ±125 ppm at I=3.0.
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  • 3
    ISSN: 1572-8927
    Keywords: Tri-n-octylphosphine oxide ; haloalkanes ; infinite dilution activity coefficients ; molecular association ; gas chromatography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The gas chromatographic retention behavior of nineteen halogenated hydrocarbons and of seven saturated hydrocarbons was measured at four temperatures from 55 to 65°C in tri-n-octylphosphine oxide (TOPO) and at 60°C in squalane (SQ). Thermodynamic functions of solution in TOPO were computed from these data. Strongly negative deviations from the ideal behavior were interpreted in terms of halogenated hydrocarbon+TOPO association, and the equilibrium constants were calculated by reference to the inert solvent SQ. The larger equilibrium constants correspond to solutes with a definite proton donor capability. The substitution of Cl for Br, however, produces an increase in the association constants suggesting the existence of other interaction mechanisms. Complexing of halogenated hydrocarbons with TOPO is markedly greater than with ethers, thioethers or tertiary amines.
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  • 4
    ISSN: 1572-8927
    Keywords: Donor number estimation ; oxygen- and nitrogen-containing solvents ; chloroform ; proton NMR solvent shift ; solvent basicity scale
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A linear correlation was determined for oxygen- and nitrogen-containing solvents between the proton NMR shift of chloroform, dilute in a solvent, and the donor number (DN) of that solvent. Results are given for water and for 13 organic solvents. The best straight line is given by DN=7.4–16.6Δδ (CHCl 3 ) where Δδ (CHCl 3 ) is the shift of pure chloroform relative to that of chloroform in dilute solution. Donor numbers of several solvents were estimated from the correlation.
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  • 5
    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.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 14 (1985), S. i 
    ISSN: 1572-8927
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
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  • 7
    ISSN: 1572-8927
    Keywords: Hydrogen bonding ; alcohols ; amines ; thermodynamics ; calorimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The pure base calorimetric method has been used to determine the enthalpies of hydrogen bond complex formation between aliphatic amines and alcohols. The enthalpies of complexation for the series methanol-n-butanol bonding with triethylamine increase with decreasing alkyl chain length in accordance with the electron donating properties of alkyl groups. Unexpectedly, the enthalpies for the complexes of n-butanol with tributylamine, tripropylamine, and triethylamine increase with decreasing alkyl chain length. Primary and secondary amines form hydrogen bonded complexes with n-butanol in which the amine protons form an NH···O bond with the alcohol and the alcohol hydroxyl proton donates a proton to the amine nitrogen. The difference in enthalpy of complex formation between tertiary amines and secondary amines is largely accounted for by the involvement of the amine proton of the secondary amine. Primary amines, like secondary amines, donate only one proton to the complex with n-butanol but have a larger complex enthalpy than secondary amines probably because of steric hindrance and differences in basicity.
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  • 8
    ISSN: 1572-8927
    Keywords: Speed of sound ; aqueous electrolytes ; compressibility ; sea salts ; NaCl ; Na2SO4 ; MgCl2 ; MgSO4
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The speed of sound of mixtures of the six possible combinations of the major sea salt ions (Na+, Mg2+, Cl−, and SO 4 2− ) have been determined at I=3.0 and at 25°C. The results have been used to determine the changes in the adiabatic compressibility of mixing ΔKm the major sea salts. The values of ΔKm have been fit to the equation ΔKm=y2y3I2[k0+k1(1-2y3)] where yi is the ionic strength fraction of solute i, k0 and k1 are parameters related to the interactions of like-charged ions. The Young cross-square rule is obeyed to within ±0.04×10−6 cm3-kg−1-bar−1. A linear correlation was found between the compressibility k0 and volume v0 interaction parameters (104k0=−0.24+3.999 v0, s=0.15) in agreement with out earlier findings. Estimates of the sound speeds for the cross square mixtures (NaCl+MgSO4 and MgCl2+Na2SO4) were made using the equations of Reilly and Wood. The estimated sound speeds were found to agree on the average with the measured values to ±0.36 m-sec−1.
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  • 9
    ISSN: 1572-8927
    Keywords: Sugars ; hydrophobicity ; partition coefficient ; polystyrene gel ; CH-dense surface ; transfer free energy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Partition coefficients K av for the partition of sugars between a polystyrene gel and aqueous solvents were determined. The results show that monosaccharides have different affinities for polystyrene. Their K av values increase markedly in NaCl solution but reduce to nearly the same value in solutions of NaSCN and LiSCN, both highly chaotropic salts. The K av of maltodextrins increase with their molecular weight. These partition peculiarities are attributed to the hydrophobic nature of sugars presumably due to their CH surface. The order of increasing hydrophobicity based on K av is: D-galactose 〈 D-glucose 〈 D-mannose 〈 (D-arabinose, D-xylose) 〈 D-ribose. This order is consistent with that based on the free energy change pertaining to the transfer of sugar molecules from water to 1-butanol.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 14 (1985), S. 139-140 
    ISSN: 1572-8927
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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