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  • Articles  (68)
  • Springer  (67)
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  • Articles  (68)
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  • 1
    Electronic Resource
    Electronic Resource
    The partial molal volume and compressibility change for the formation of the calcium sulfate ion pair at 25°C (1977)
    Springer
    Journal of solution chemistry 6 (1977), S. 269-280 
    Details
    ISSN: 1572-8927
    Keywords: Calcium sulfate ; molal volume and compressibility ; ion pair
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The apparent molal volumes (φv) and compressibilities (φK) of CaSO4 solutions have been determined at 25°C from precise density and sound-speed measurements. The large deviations of the values of φv and φK from the limiting law and various additivity estimates for the free ions (Ca2+, SO 4 2− ) have been used to estimate the partial molal volume ( $$\Delta \bar V^\circ $$ ) and compressibility ( $$\Delta \bar K^\circ $$ ) for the formation of the CaSO 4 0 ion pair. Values of $$\Delta \bar V^\circ $$ = 25 ± 3 cm3-mole−1 and $$\Delta \bar K^\circ $$ = (54±21)×10−4 cm3-mole−1-bar−1 were found. Since these values are larger than the value for the formation of MgSO 4 0 , the results indicate that more inner-sphere ion pairs are formed when SO 4 2− complexes with Ca2+ than with Mg2+. Using a simple model for ion-water interactions, the percent of inner-sphere or contact ion pairs in CaSO4 solutions is estimated to be 36 to 37%.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00645458
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  • 2
    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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  • 3
    Electronic Resource
    Electronic Resource
    The enthalpies of dilution of phosphate solutions at 30°C (1978)
    Springer
    Journal of solution chemistry 7 (1978), S. 877-889 
    Details
    ISSN: 1572-8927
    Keywords: Ionization of phosphoric acid ; enthalpy of dilution ; phosphate solutions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The enthalpies of dilution of aqueous solutions of HCl, H3PO4, NaOH, NaH2PO4, Na2HPO4 and Na3PO4 in the molality range 0.1 to 1.0 mole-kg−1 have been determined at 30°C. The relative apparent molal enthalpies φL of HCl, NaOH, NaH2PO4 and Na2HPO4 have been determined with the aid of an extended form of the Debye-Hückel limiting law. The relative apparent molal enthalpies for Na3PO4 solutions have been corrected for hydrolysis. A value of ΔH H o =9525±150 cal-mole−1 was determined for the heat of hydrolysis of PO 4 −3 . This value gives ΔH 3 o =3815±150 cal-mole−1 for the ionization of H2PO 4 − , which is in good agreement with the value of ΔH 3 o =3500±500 cal-mole−1 determined directly by Pitzer at 25°C. The relative apparent molal enthalpies for H3PO4 solutions have been corrected for ionization. A value of ΔH 1 o =−1900±150 cal-mole−1 was obtained for the heat of ionization of H3PO4 to H++H2PO 4 − . This value is in good agreement with the value of ΔH 1 o =−2031 cal-mole−1 at 30°C determined by Harned and Owen from the temperature coefficient of the equilibrium constant and ΔH 1 o =−1950±80 cal-mole−1 at 25°C determined from calorimetry by Pitzer.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00645297
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  • 4
    Electronic Resource
    Electronic Resource
    The Activity Coefficients of HCl in HCl–Na2SO4 Solutions from 0 to 50°C and Ionic Strengths Up to 6 Molal (1997)
    Springer
    Journal of solution chemistry 26 (1997), S. 31-45 
    Details
    ISSN: 1572-8927
    Keywords: Activity coefficient ; electromotive force ; Pitzer ; HCl ; Na2SO4 ; NaHSO4
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The electromotive force of HCl–Na2SO4 solutions has been determined from 5 to 50°C and ionic strengths from 0.5 to 6m with a Harned type cell $${\text{Pt; H}}_{\text{2}} ({\text{g, 1 atm}})|{\text{HCl(}}m_1 {\text{) + Na}}_{\text{2}} {\text{SO}}_{\text{4}} {\text{(}}m_2 {\text{)}}|{\text{AgCl, Ag}}$$ The results have been used to determine the activity coefficient of HCl in the mixtures. The activity coefficients have been analyzed with the Pitzer equations to account for the ionic interactions. The measurements were used to determine interaction coefficients (β0, β1) for NaHSO4 solutions from 5 to 50°C. The model represents the mean activity coefficients of HCl in the mixtures to ±0.005 over the entire temperature and concentration range of the measurements. The results have been combined with literature data to provide parameters that are valid from 0 to 250°C for NaHSO4 solutions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1024433011426
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  • 5
    Electronic Resource
    Electronic Resource
    A high-precision, variable-pressure magnetic float densimeter (1972)
    Springer
    Journal of solution chemistry 1 (1972), S. 173-186 
    Details
    ISSN: 1572-8927
    Keywords: High pressure ; float densimeter
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A simple, versatile, magnetic float densimeter that can be used at high pressures (1200 bars) to measure the density of liquids is described. The system has been calibrated with water at 25°C from 1 to 1200 bars, demonstrating a sensitivity of 0.5 ppm and a precision of 11 ppm. The accuracy of the densimeter has been verified by measuring the densities of NaCl solutions at 25°C and from 1 to 1200 bars. Excellent agreement with previously published data was achieved.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01028453
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  • 6
    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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  • 7
    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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  • 8
    Electronic Resource
    Electronic Resource
    The effect of pressure on the ionization of boric acid in aqueous solutions from molal-volume data (1974)
    Springer
    Journal of solution chemistry 3 (1974), S. 417-430 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00651533
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  • 9
    Electronic Resource
    Electronic Resource
    Molal volume of aqueous boric acid-sodium chloride solutions (1974)
    Springer
    Journal of solution chemistry 3 (1974), S. 431-444 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00651534
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  • 10
    Electronic Resource
    Electronic Resource
    The enthalpy of formation of magnesium sulfate ion pairs (1975)
    Springer
    Journal of solution chemistry 4 (1975), S. 145-159 
    Details
    ISSN: 1572-8927
    Keywords: Enthalpy ; dilution ; ion pairs ; lithium, sodium, and potassium chlorides and sulfates
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The enthalpies of dilution of lithium, sodium, potassium, and magnesium chloride and sulfate solutions in the range 0.1 to 1.0 m have been measured at 30°C with a microcalorimeter. The relative apparent enthalpies φL of these solutions have been determined with the aid of an extended form of the Debye-Hückel limiting law $$\phi _L = S_H I^{1/2} [1/(1 + I^{1/2} ) - (\sigma /3)] + {\rm B}{\rm I} + CI^{3/2} $$ whereS H is the limiting-law slope, σ = 3/I3/2 × [(1+I1/2 − 1/(1+I1/2 − 2 ln (2+I1/2)], andB andC are empirical constants. This equation fits the experimental results to within a standard deviation of 2 cal-mole−1 for all the salts. The measured φL for the MgSO4 solutions were compared to those calculated using the additivity principle, φL(MgCl2) + φL(Na2SO4) − 2φL(NaCl), and the extended Debye-Hückel equation. The results of this comparison have been used to calculate the ΔH A o for the formation of MgSO 4 0 . A value of ΔH A o = 1.15 to 1.36 was obtained, depending upon the φL estimates for the free ions Mg2+ and SO 4 2− . The results are briefly discussed and compared to the results obtained by other workers.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00649155
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