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  • Pitzer theory  (3)
  • molal volume  (3)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 1 (1972), S. 309-327 
    ISSN: 1572-8927
    Keywords: Effect of pressure ; ionization of water ; molal volume
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The apparent molal volumes of dilute (0.002 to 1.0m) aqueous HCl and NaOH solutions have been determined at 0, 25, and 50°C and NaCl solutions at 50°C. The partial molal volumes ( $$\bar V$$ ) of HCl, NaOH, and NaCl solutions have been determined from these apparent molal volumes and other reliable data from the literature. The partial-molal-volume changes ( $$\Delta \bar V_1 $$ ) for the ionization of water, H2O→H++OH−, have been determined from 0 to 50°C and 0 to 1m ionic strength from the partial molal volumes of HCl, NaOH, NaCl, and H2O. The partial molal compressibilities ( $$\bar K$$ for HCl, NaOH, NaCl, and H2O have been estimated from data in the literature and used to determine the partial molal compressibility changes ( $$\Delta \bar K_1 $$ ) for the ionization of water from 0 to 50°C and 0 to 1m ionic strength. The effect of pressure on the ionization constant of water has been estimated from partial-molal-volume and compressibility changes using the relation $$RTln(K^P /K) = - \Delta \bar V(P - 1) + \tfrac{1}{2}\Delta \bar K(P - 1)^2 $$ from 0 to 50°C and 0 to 2000 bars. The results agree very well with the directly measured values.
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  • 2
    ISSN: 1572-8927
    Keywords: Densities ; partial molal volumes ; KCl ; K2SO4 ; Pitzer theory
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The densities of KCl and K2SO4 were measured from dilute solutions to saturation from 5 to 95°C. The data were combined with literature data to produce density and apparent molal volume, Vφ, equations from 0 to 100°C and to saturation. The standard deviations of the density equations were 30×10−6 g-cm−3 and 32×10−6 g-cm−3, respectively, for KCl and K2SO4. Pitzer equations were used to fit the Vφ data. The resulting infinite dilute partial molal volumes, Vo, were in reasonable agreement with literature data. The densities of the mixtures of the six combinations of the salts KCL, K2SO4 NaCl and Na2SO4 were measured at I=2.0 and t=5, 25, 55 and 95°C. The resulting volumes of mixing were fitted to equations of the form $$\Delta V_m = y(1 - y)I^2 [\nu _0 + \nu _1 (1 - 2y)]$$ wherev 0 andv 1 are interaction parameters. The cross square rule is valid over the entire temperature range although the deviations are larger at higher temperatures. Pitzer θ NaK v and $$\theta _{ClSO_4 }^v $$ parameters were determined from the common ion mixtures. The values of θ NaK v were small and not strongly dependent upon temperature. The values of $$\theta _{ClSO_4 }^v $$ were also small and changed considerably with temperature.
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  • 3
    ISSN: 1572-8927
    Keywords: Densities ; partial molal volumes ; NaCl ; Na2SO4 ; MgCl2 ; MgSO4 ; Pitzer theory
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The densities of the major sea salts (NaCl, Na2SO4, MgCl2, and MgSO4) have been measured from 25 to 95°C and to saturation. These results have been combined with literature data and fitted to equations of the form $$\Delta d = Am{\text{ }} + {\text{ }}Bm^{3/2} {\text{ }} + {\text{ }}Cm^2 {\text{ }} + {\text{ }}Dm^{5/2} $$ where Δd=d−do (do is the density of water) and A, B, and C, etc., are polynomial functions of temperature. The standard deviations of the fits were better than ±50×10−6 g-cm−3 for all the salts from 0 to 95°C and to saturation. The apparent molal volumes Vϕ of the salts have been fitted to the equations of Pitzer. The infinite dilution values of Vϕ were in good agreement with literature data, provided the results were not overfit. The large deviations of Vϕ for MgSO4 from additivity as a function of concentration were attributed to the formation of MgSO4 ion pairs.
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  • 4
    ISSN: 1572-8927
    Keywords: Sound speeds ; compressibilities ; partial molal compressibilities ; NaCl ; Na2SO4 ; MgCl2 ; MgSO4 ; Pitzer theory
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The sound velocities of aqueous NaCl, Na2SO4, MgCl2, and MgSO4 solutions were measured from 25 to 95°C in 10o intervals from dilute to saturated solutions. The results were combined with our earlier data and fitted to functions of molality and temperature to within ±0.4 m-sec−1. The adiabatic compressibilities βS were calculated from sound speeds and used to calculate the adiabatic apparent molal compressibilities ξφ. Isothermal compressibilities β and isothermal apparent molal compressibilities χφ were calculated from βS using literature values for the expansibilities and heat capacities. The values of χφ were extrapolated to infinite dilution using the Debye-Huckel limiting law to determine partial molal compressibilities. The apparent molal compressibilities were fitted to Pitzer's equations. The Pitzer parameters for the concentration dependence of χφ were determined as a function of temperature. Correlations of χφ and Vφ at various temperatures were found for the electrolytes.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 3 (1974), S. 417-430 
    ISSN: 1572-8927
    Keywords: Ionization of boric acid ; molal volume ; effect of pressure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The apparent, φ v , and partial, $$\bar V_2 $$ molal volumes of dilute (0.02 to 0.7m) aqueous boric acid, B(OH)3, and sodium borate, NaB(OH)4, solutions have been determined from 0 to 50° C from precision density measurements. The φ v of boric acid is a linear function of the first power of concentration. For sodium borate, the Debye-Hückel theoretical limiting law slope for the φ v as a function of the square root of molar concentration is approached at all temperatures studied. The positive deviations at higher concentrations increase with decreasing temperature. The infinite-dilution volume properties of both B(OH)3 and NaB(OH)4 indicate that these solutes behave like “structure breakers” between 0 and 50°C (that is ∂2φ v ° /∂T2 is negative). The volume change for the ionization of boric acid in water $$\Delta \bar V^\circ $$ , is calculated from the volume data at various temperatures. This volume change has been used to estimate the effect of pressure on the ionization of boric acid solutions from 0 to 50°C and 0 to 1000 bars. The calculated effect of pressure on the ionization is in good agreement with direct measurements.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 3 (1974), S. 431-444 
    ISSN: 1572-8927
    Keywords: Boric acid ; molal volume ; nonelectrolyte-electrolyte mixture ; volumes of mixing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The apparent molal volume φ v of boric acid has been determined in various sodium chloride solutions at 0 and 25°C from precise density measurements. Similar to its behavior in pure water, the φ v of boric acid in NaCl solutions is a linear function of the concentration. The infinite dilution φ v ° and the slope S v * of B(OH)3 are larger in NaCl solutions than in pure water. NaCl appears to be able to dehydrate B(OH)3 and cause an increase in B(OH)3-B(OH)3 interactions. The mean apparent molal volumes Φ v of the B(OH)3−NaCl solutions are predicted from pure water data using a modification of Young's rule for electrolyte-nonelectrolyte mixtures and are compared to the directly measured values. A similar treatment was carried out on the density data of acetic acid-sodium chloride solutions. The modified Young's rule was found to give a good first approximation of the mean apparent molal volumes of nonelectrolyte-electrolyte systems. The deviations from the Young's rule approximation are studied as excess volumes of mixing boric acid and NaCl solutions.
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