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  • Equilibrium constant  (2)
  • Springer  (2)
  • American Institute of Physics (AIP)
  • American Physical Society (APS)
  • The American Society for Biochemistry and Molecular Biology (ASBMB)
  • 1
    ISSN: 1572-8927
    Keywords: Equilibrium constant ; enthalpy change ; entropy change ; heat capacity change ; flow calorimetry ; high temperature ; magnesium chloride ; calcium chloride ; hydrochloric acid ; ion association ; isocoulombic reaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The aqueous reactions, Mg2++Cl−=MgCl+, Ca2++Cl−=CaCl+, and H+ +Cl−=HCl(aq), were studied as a function of ionic strength at 250, 275, 300, and 325°C using a flow calorimetric technique. The logK, ΔH, ΔS and ΔCp values were determined from the fits of the calculated and experimental heast. The data were reduced assuming a known functionality of the activity coefficient. Hence, the logK, ΔH, ΔS and ΔCp values determined in this study are dependent on the activity coefficient model used. These thermodynamic values were compared with literature results. The logK values for the formation of MgCl+ agree reasonably well with those reported in the literature. The logK values for CaCl+ formation agree reasonably well with those reported in the literature at 300 and 325°C. At lower temperatures, the agreement is poorer. The logK values for the formation of HCl(aq) are generally lower than those reported in the literature. The logK, ΔH, ΔS and ΔCp values for all three ion association reactions are positive and increase with temperature over the temperature range studied. These values are the first determined calorimetrically for the formation of MgCl+ and CaCl+ in the temperature range 275–325°C.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-8927
    Keywords: Equilibrium constant ; enthalpy change ; entropy change ; heat capacity change ; flow calorimetry ; high temperature ; nitric acid ; ion association ; isocoulombic reaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The aqueous reaction, HNO3(aq)=H++NO 3 − was studied as a function of ionic strength I at 250, 275, 300 and 319°C using a flow calorimeter and the equilibrium constant K and enthalpy change (ΔH) at I=0 were determined. Using these experimental values, equations describing logK, ΔH, the entropy change ΔS and the heat capacity change ΔC p of reaction at I=0 and temperatures from 250 to 319°C were derived. The increasing importance of ion association as temperature rises was discussed. The use of an equation containing identical numbers of positive and identical numbers of negative charges on both sides of the equal sign (isocoulombic reaction principle) was applied to the logK values reported here and to those determined by others. The resulting plot of logK for the isocoulombic reaction vs. 1/T was fairly linear which supports the postulate that the principle is a useful technique for the extrapolation of logK values from low to high temperatures.
    Type of Medium: Electronic Resource
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