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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Environmental science & technology 29 (1995), S. 289-301 
    ISSN: 1520-5851
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Environmental science & technology 29 (1995), S. 818-824 
    ISSN: 1520-5851
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Aquatic geochemistry 1 (1995), S. 53-88 
    ISSN: 1573-1421
    Keywords: Anoxic waters ; the Framvaren fjord
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract In the summer of 1993, a number of chemical parameters (H2S, O2, pH, TA, TCO2, NH 4 + , PO 4 3− , SiO2, Mn2+ and Fe2+) were measured in the Framvaren Fjord, a permanently super-anoxic fjord in southern Norway. The extremely steep gradient of sulfide near the interface suggests that other than downward flux of oxygen, three other possible oxidants, particulate manganese and iron oxides, phototrophic sulfur oxidation bacteria and horizontally transported oxygen account for the oxidation of the upward flux of H2S. Water intrusion through the sill accounts for the temperature inflection above the interface, which, together with internal waves (Stigerbrandt and Molvaer, 1988), may cause fluctuations of the depth of interface. Significant gradients of hydrographic properties and chemical species between 80–100 m suggest that there is a “second interface” at about 90 m that separates the deep and older bottom waters. A stoichiometric model is applied to examine the biogeochemical cycles of S, C, N and P in the Framvaren. High C:S, C:N and C:P ratios are found while the nutrients (N, P) have Redfield ratio. Based on the C:N:P ratio of 155:16:1 in organic matter, about 30% of sulfide produced by sulfate reduction is estimated to be removed by processes such as oxidation, formation of FeS2, degassing and incorporation into organic matter. The rates of oxidation of H2S by Mn and Fe oxides in the water near the interface were slightly faster than the observed values in the laboratory, probably due to the presence of bacteria.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Aquatic geochemistry 4 (1998), S. 1-2 
    ISSN: 1573-1421
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Aquatic geochemistry 4 (1998), S. 153-199 
    ISSN: 1573-1421
    Keywords: Activity coefficients ; activity ; ions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract This paper reviews the present status of the Pitzer chemical equilibrium model, which can be used to characterize the one-atmosphere activity coefficients of ionic and non-ionic solutes in natural waters as a function of temperature and ionic strength. The model considers the ionic interactions of the major seasalt ions (H, Na, K, Mg, Ca, Sr, Cl, Br, OH, HCO3, B(OH)4, HSO4, SO4, CO3, CO2, B(OH)3, H2O) and is based on the 25 °C model of Weare and co-workers. The model has been extended by a number of workers so that reasonable estimates can be made of the activity coefficients of most of the major seasalt ions from 0 to 250 °C. Recently coefficients for a number of solutes that are needed to determine the dissociation constants of the acids from 0 to 50 °C (H3CO3, B(OH)3, H2O, HF, HSO 4 - , H3PO4, H2S, NH 4 + etc.) have been added to the model. These results have been used to examine the carbonate system in natural waters and determine the activity of inorganic anions that can complex trace metals. The activity and osmotic coefficients determined from the model are shown to be in good agreement with measured values in seawater. This model can serve as the foundation for future expansions that can examine the activity coefficient and speciation of trace metals in natural waters. At present this is only possible from 0 to 50 °C over a limited range of ionic strengths (〈1.0) due to the limited stability constants for the formation of the metal complexes. The future work needed to extend the Pitzer model to trace metals is discussed.
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  • 6
    ISSN: 1573-1421
    Keywords: dependence on medium of hydrolysis constants ; ΔH° for the hydrolysis of (CH3)2Sn2+ ; hydrolysis of (CH3)2Sn2+ ; Pitzer interaction parameters ; speciation of (CH3)2Sn2+ in natural waters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Hydrolysis constants of dimethyltin(IV) cation, in different salt solutions (CaCl2: 0.15 ≤ I ≤ 0.90; MgCl2: 0.30 ≤ I ≤ 0.60; NaCl-–NaClO4, NaCl-–NaNO3 mixtures: I = 3; NaCl-–Na2SO4 mixtures: I = 1 mol dm-3) were determined by potentiometric ([H+]-glass electrode) measurements. These data, together with previous data (De Stefano et al., 1996b) were interpreted in terms of DHT (Debye–Hückel type) and Pitzer equations. The mixed electrolyte solution results also allowed us to obtain Θ and Ψ parameters for the Pitzer equation. Calorimetric measurements were made at different ionic strengths in order to find the temperature dependence of hydrolysis constants and of the relative interaction parameters. The body of results allows us to determine the speciation of natural waters in a wide range of ionic strengths and temperatures.
    Type of Medium: Electronic Resource
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  • 7
    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.
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  • 8
    ISSN: 1572-8927
    Keywords: Activity coefficient ; electromitive 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 $$Pt; H_2 (g, 1 atm)|HCl(m_1 ) + Na_2 SO_4 (m_2 )|AgCl, Ag$$ The results have been used to determine the activity coefficient of HCl in the mixtures. The activity coefficiencts 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 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
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 28 (1999), S. 849-864 
    ISSN: 1572-8927
    Keywords: Apparent molar heat capacities ; partial molar heat capacities ; Pitzer's equations ; lanthanide elements ; transition metals ; alkali metal sulfates ; magnesium sulfate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Apparent molar heat capacities C p,φ for 71 rare earth chlorides, nitrates, and perchlorates, alkaline earth and transition metal chlorides, nitrates, and perchlorates, and alkali metal carbonates and sulfates have been fitted to the Pitzer equation for heat capacities. The apparent molar heat capacities at infinite dilution $$C_{{\text{p,}}\Phi }^{\text{o}} $$ (equal to the standard partial molar heat capacity, $$\overline C _{{\text{p,2}}}^{\text{o}} $$ ) were used to evaluate a set of “best” ionic heat capacities, from which improved values of $$C_{{\text{p,}}\Phi }^{\text{o}} $$ for the electrolytes were calculated. These were then used in the Pitzer equation to reevaluate the higher Pitzer coefficients. The Pitzer coefficients so evaluated can express, in most cases, the behavior of C p,φ within experimental error from infinite dilution to the upper limit of the data. Ionic heat capacities have been correlated with the absolute entropies of the ions by statistically assigning the ionic heat capacities to obtain the best linear fit.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 28 (1999), S. 959-972 
    ISSN: 1572-8927
    Keywords: Hydrolysis of trimethyltin(IV) ; hydrolysis constants ; enthalpy of hydrolysis ; dependence on ionic strength ; Pitzer interaction parameters ; speciation of trimethyltin(IV)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The hydrolysis of trimethyltin(IV) has been studied by potentiometry (H+ -glass electrode) and calorimetry in various salt media (NaNO3, NaCl, KCl, Na2SO4, and NaNO3—NaCl mixtures). The effect of ionic strength on the hydrolysis constants is accounted for by a simple Debye–Hückel type equation and by Pitzer equations. The results allow us to obtain ΔH for hydrolysis and the temperature dependence of the Pitzer parameters. The resulting coefficients can be used to examine the speciation of (CH3)3Sn+ in multicomponent electrolyte solutions, such as natural waters, over a wide range of temperature and ionic strength.
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