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  • 1
    Electronic Resource
    Electronic Resource
    The effect of pressure on the ionization of water at various temperatures from molal-volume data1 (1972)
    Springer
    Journal of solution chemistry 1 (1972), S. 309-327 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00715990
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  • 2
    Electronic Resource
    Electronic Resource
    PVT properties of concentrated aqueous electrolytes. II. Compressibilities and apparent molar compressibilities of aqueous NaCl, Na2SO4, MgCl2, and MgSO4 from dilute solution to saturation and from 0 to 50°C (1982)
    Springer
    Journal of solution chemistry 11 (1982), S. 671-686 
    Details
    ISSN: 1572-8927
    Keywords: sound speeds ; compressibilities ; partial molar compressibilities ; NaCl ; Na2SO4 ; MgCl2 ; MgSO4 ; equations of state
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The relative sound velocities (U-U°) of aqueous NaCl, Na2SO4, MgCl2, and MgSO4 solutions were measured from 0.05m to saturation and from 0 to 45°C. The sound speeds were combined with our earlier work and fitted to a function of molality and temperature to standard deviations within 0.3 m-sec−1. The adiabatic compressibilities, βs, were determined from the sound speeds and used to calculate adiabatic apparent molar compressibilities, Kϕ,s, isothermal compressibilities, β, and apparent molar compressibilities, Kϕ, were determined from the adiabatic values using literature data for expansibilities and heat capacities. The values of Kϕ have been extrapolated to infinite dilution using an extended limiting law. The resulting K0 at various temperatures are in reasonable agreement with literature values. The results of this study have been combined with our earlier results to derive a secant bulk modulus equation of state for NaCl, Na2SO4, MgCl2, and MgSO4 solutions valid from 0 to 50°C and 0 to 1000 bar.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00645335
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  • 3
    Electronic Resource
    Electronic Resource
    The ionization of carbonic acid in Na-Mg-Cl solutions at 25°C (1983)
    Springer
    Journal of solution chemistry 12 (1983), S. 401-412 
    Details
    ISSN: 1572-8927
    Keywords: Carbonic acid ; ionization ; Pitzer parameters ; weak acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The stoichiometric pK2 * and pK2 * for the ionization of carbonic acid has been determined from emf measurements in NaCl solutions with small amounts of MgCl2 from I=0.5 to 6.0 molal at 25°C. Our results at low ionic strengths (I=0.7) are in agreement with the measurements of Dyrssen and Hansson and Pytkowicz and Hawley. Our results have been analyzed using the ion pairing model and Pitzer's specific interaction equations. From the values of pK1 *, we have determined the Pitzer parameters β0[Mg (HCO3)2] = 0.0193 and β1[Mg (HCO3)2] = 0.0193 which reproduces the pK1 * results to ±0.01. The values of pK2 * were used to determine β0(MgCO3) = 2.833, β1(MgCO3) = -15.069, β2(MgCO3) = -204.90 and Cϕ (MgCO3)=−0.970 which reproduces the pK2 *′ s to ±0.02. The pK2 * results could be reproduced to the same precision with fewer parameters using the ion pairing model [pK(MgCO3)=3.00 and log γ (MgCO3)=0.0560 I].
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00646393
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  • 4
    Electronic Resource
    Electronic Resource
    PVT properties of concentrated aqueous electrolytes. III. Volume changes for mixing the major sea salts at I=1.0 and 3.0 at 25°C (1985)
    Springer
    Journal of solution chemistry 14 (1985), S. 837-851 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00646294
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  • 5
    Electronic Resource
    Electronic Resource
    The PVT properties of concentrated aqueous electrolytes. IV. Changes in the compressibilities of mixing the major sea salts at 25°C (1985)
    Springer
    Journal of solution chemistry 14 (1985), S. 853-864 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00646295
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  • 6
    Electronic Resource
    Electronic Resource
    The PVT properties of concentrated aqueous electrolytes. VIII. The volume changes for mixing the major sea salts at an ionic strength of 3.0 from 5 to 95°C (1987)
    Springer
    Journal of solution chemistry 16 (1987), S. 491-502 
    Details
    ISSN: 1572-8927
    Keywords: Sea salts ; NaCl ; Na2SO4 ; MgSO4 ; MgCl2 ; volumes of mixing ; densities ; cross-square rule
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The densities of mixtures of the six possible combinations of the four major sea salts (NaCl, Na2SO4, MgCl2, and MgSO4) have been measured at a constant ionic strength of I=3.0 at the temperatures 5, 25, 55, and 95°C. The results have been used to determine ΔVm, the volume change for mixing the major sea salts, which were fitted to equations of the from $$\Delta V{\text{m = }}y2y3I^2 \left[ {v0 + v1\left( {1 - 2y{\text{3}}} \right)} \right]$$ where y1 is the molal ionic strength fraction of solute i, and vo and v1 are parameters related to the interaction of like-charge ions. The cross-square rule was verified at each of the temperatures of study, but the rule did not hold as well at the higher temperatures. The temperature dependence of the volume change for mixing ΔVm was examined for each of the six mixtures. It was found that the two mixtures NaCl−Na2SO4 and MgSO4−MgCl2 showed little or no variation of ΔVm with temperature, while the other mixtures showed considerable temperature dependence. These results indicate that the anion-anion interactions of Cl− and SO 4 2− do not vary with temperature, while the cation-cation interactions of Na+ and Mg2+ are temperature sensitive. Explanations for these results based on ion-water inter actions are presented.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00648598
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  • 7
    Electronic Resource
    Electronic Resource
    The dissociation of phosphoric acid in NaCl and NaMgCl solutions at 25°C (1989)
    Springer
    Journal of solution chemistry 18 (1989), S. 875-891 
    Details
    ISSN: 1572-8927
    Keywords: Phosphoric acid ; Pitzer equations ; ion pairing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The pK 1 * , pK 1 * and pK 3 * for the dissociation of H3PO4 have been measured in NaCl solutions from 0.5 to 6m at 25°C. The results have been used to evaluate Pitzer interaction parameters ψ(NaClH2PO4)=−0.028±0.005, λ(NaH3PO4)=−0.075±0.025, θ(HPO4Cl)=0.105±0.009, θ(PO4Cl)=−0.59±0.02 and ψ(NaClHPO4)=−0.003±0.004, ψ(PO4NaClH)=0.110±0.008. These parameters yield values of pK 1 * , pK 2 * and pK 3 * in NaCl that agree with the measured values with average deviations of ±0.04, ±0.03 and ±0.05 in pK 1 * . Measurements of pK 1 * and pK 2 * were also made in NaMgCl solutions. These results have been used to evaluate β(O)(MgH 2 PO 4)=−3.55±0.07,β(1)(MgH 2 PO 4=−16.9±0.03, β(O)(MgH 2 PO 4=−17.5±0.03 and β(1)(MgH 2 PO 4)=27.4±0.8 at 25°C. The results for pK 2 * in NaMg−Cl solutions were also used to calculate log K MX * =3.2±0.1 for the formation of the ion pair MgHPO 4 o .
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00685063
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  • 8
    Electronic Resource
    Electronic Resource
    Equilibrium constants for the formation of Cu(I) halide complexes (1990)
    Springer
    Journal of solution chemistry 19 (1990), S. 375-390 
    Details
    ISSN: 1572-8927
    Keywords: Equilibrium constants ; CuCl ; CuBr ; complexes ; Pitzer equations ; spectral data
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The stoichiometric equilibrium constants, K 3 * , for the formation of CuX 3 2− from CuX 2 − +X− where X=Cl and Br, have been determined from spectral measurements. The measurements were made in NaCl and NaBr solutions from I=0.5 to 6.0m at 5, 25 and 45°C. The measured constants were extrapolated to infinite dilution using the Pitzer equations. The Pitzer parameters, β0, β1 and Cφ, for the interaction of Na+ with CuX 2 − and CuX 3 2− are briefly discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00648142
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  • 9
    Electronic Resource
    Electronic Resource
    The PVT properties of concentrated aqueous electrolytes IX. The volume properties of KCl and K2SO4 and their mixtures with NaCl and Na2SO4 as a function of temperature (1990)
    Springer
    Journal of solution chemistry 19 (1990), S. 353-374 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00648141
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  • 10
    Electronic Resource
    Electronic Resource
    The volume and compressibility change for the formation of the LaSO 4 + ion pair at 25°C (1977)
    Springer
    Journal of solution chemistry 6 (1977), S. 589-607 
    Details
    ISSN: 1572-8927
    Keywords: Lanthanum sulfate ; magnetic float densimeter ; sound velocimeter ; density ; apparent molal volume ; adiabatic apparent molal compressibility ; ion pair ; electrostriction ; hydration number
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The apparent molal volumes (φv) and adiabatic compressibilities [φK(S)] of La2(SO4)3 solutions have been determined from density and sound speed data at 25°C. The large positive deviations of φv and φK(S) of La2(SO4)3 from the limiting law have been attributed to the formation of the ion pair LaSO 4 + . The observed values of φv and φK(S) have been used to estimate the change in the apparent molal volume and adiabatic compressibility for the formation of LaSO 4 + from $$\Delta \phi (LaSO_4^ + ) = [\phi (obs.) - \phi (2La^{3 + } ,3SO_4^{2 - } )]/\alpha$$ where ϕ(2La3+, 3SO 4 2− ) is the apparent molal volume or adiabatic compressibility of the free ions, and α is the degree of association. The value of $$\Delta \phi _v^o (LaSO_4^ + ) = \Delta \bar V^o (LaSO_4^ + ) = 22.8 \pm 1cm^3 - mole^{ - 1}$$ and $$\Delta \phi _{K(S)}^o (LaSO_4^ + ) = \Delta \bar K_S^o (LaSO_4^ + ) = 85 \pm 20 \times 10^{ - 4} cm^3 - mole^{ - 1} - bar^{ - 1}$$ at infinite dilution are in reasonable agreement with the values determined from the high-pressure conductance data of Fisher and Davis. The number of hydrated water molecules (ca. 11) associated with the formation of LaSO 4 + determined from the volume and compressibility data are in good agreement.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00655373
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