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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 7 (1978), S. 373-383 
    ISSN: 1572-8927
    Keywords: Ferric ; hydrolysis ; ionic strength ; temperature ; enthalpy ; ferric hydroxide ; ultraviolet ; spectroscopic
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ultraviolet absorbance spectra of ferric ions in 0.68m NaClO4 were studied as a function of pH at 4.0, 14.9, and 25.0°C. The results provided an evaluation of the stability constant for the formation of FeOH2+ which is *β1=[FeOH +][H +]/[Fe 3+]. The enthalpy change for the reaction Fe3++H2O⇌ FeOH2++H+ was calculated as 10.0±0.3 kcal-mole−1. Increasing temperature was also found to promote the reaction Fe3++2H2O⇌ Fe(OH) 2 + +2H+. Our results were combined with the results of other to produce an expression describing the first hydrolysis equilibrium at ionic strengths between 0 and 3m and temperatures between 4.0 and 45.0°C at 1 atm total pressure. At 25°C and 0.68m the ionic strength *β1=1.90×10-3
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 27 (1998), S. 803-815 
    ISSN: 1572-8927
    Keywords: Rare earth ; complexation ; carbonate ; ICP–MS
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Carbonate stability constants for yttrium and all rare earth elements have been determined at 25°C and 0.70 molal ionic strength by solvent exchange and inductively coupled plasma–mass spectrometry (ICP–MS). Measured stability constants for the formation of $${\text{MCO}}_3^ +$$ and $${\text{M}}\left( {{\text{CO}}_{\text{3}} } \right)_2^--$$ from M3+ are in good agreement with previous direct measurements, which involved the use of radio-chemical techniques and trivalent ions of Y, Ce, Eu, Gd, Tb, and Yb. Direct ICP–MS measurements of $${\text{MCO}}_3^ +$$ and $${\text{M}}\left( {{\text{CO}}_{\text{3}} } \right)_2^--$$ formation constants are also in general agreement with modeled stability constants for the metals La, Pr, Nd, Sm, Dy, Ho, Er, Tm, and Lu, based on linear-free energy relationship (LFER). The experimental procedures developed in this work can be used for assessing the complexation behavior of other geochemically important ligands such as phosphate, sulfate, and fluoride.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 29 (2000), S. 1089-1099 
    ISSN: 1572-8927
    Keywords: Rare earth elements ; fluoride complexation ; stability constants ; sodium perchlorate ; ionic strength ; lanthanide ; yttrium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Formation constants for the complexation of yttrium and rare earth elements(YREE) by fluoride ions have been measured at 25°C. The ionic strength (μ)dependence of YREE formation constants in perchlorate solution for ionicstrengths between 0 and 6 molar can be expressed aslogFβ1 (M, μ) =logFβ1 o (M) −3.066 μ0.5/(1 + 1.769 μ0.5)+ 0.1645 μwhere logFβ1 o(M) represents MF2+formation constants at zero ionic strength.The logFβ1 o(M) results obtained inthis work are: Y(4.46), La(3.62), Ce(3.86),Pr(3.84), Nd(3.82), Sm(4.15), Eu(4.27), Gd(4.24), Tb(4.37), Dy(4.39), Ho(4.28),Er(4.27), Tm(4.29), Yb(4.39), and Lu(4.25). The relative magnitudes of YREEformation constants are independent of ionic strength. The pattern oflogFβ1(M,μ),formation constants obtained in this work [relative magnitudes oflogFβ1 o (M)],exhibits a shallow minimum between Dy and Yb. In contrast to the smoothpattern of stability constants expected if fluoride were to interact with bare ions(with monotonically decreasing crystal radii between La and Lu), theinteractionof F− with YREEs, which have extensive hydration spheres[M(H2O)8–9 3+] resultsin a relatively complex pattern of lanthanide stability constants. The fluoridecomplexation behavior of yttrium differs distinctly from the behavior of any rareearth. Although the crystal radius of Y3;pl is approximately equalto that of Ho3+,differences in the covalence/ionicity of Y3+ relative to therare earths leads to aYF2+ stability constant that exceeds that of any rare earthelement (REE).
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Aquatic geochemistry 3 (1997), S. 345-356 
    ISSN: 1573-1421
    Keywords: boron ; boric acid ; carbonate ; CO2 system ; complexation ; spectrophotometric pH
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Boron is known to interact with a wide variety of protonated ligands(HL) creating complexes of the form B(OH)2L-.Investigation of the interaction of boric acid and bicarbonate in aqueoussolution can be interpreted in terms of the equilibrium $$B(OH)_3^0 + HCO_3^ - \rightleftharpoons B(OH)_2 CO_3^ - + H_2 O$$ The formation constant for this reaction at 25 °C and 0.7 molkg-1 ionic strength is $$K_{BC} = \left[ {B(OH)_2 CO_3^ - } \right]\left[ {B(OH)_3^0 } \right]^{ - 1} \left[ {HCO_3^ - } \right]^{ - 1} = 2.6 \pm 1.7$$ where brackets represent the total concentration of each indicatedspecies. This formation constant indicates that theB(OH)2 $$CO_3^ - $$ concentration inseawater at 25 °C is on the order of 2 μmol kg-1. Dueto the presence of B(OH)2 $$CO_3^ - $$ , theboric acid dissociation constant ( $$K\prime _B $$ ) in natural seawaterdiffers from $$K\prime _B $$ determined in the absence of bicarbonate byapproximately 0.5%. Similarly, the dissociation constants of carbonicacid and bicarbonate in natural seawater differ from dissociation constantsdetermined in the absence of boric acid by about 0.1%. Thesedifferences, although small, are systematic and exert observable influenceson equilibrium predictions relating CO2 fugacity, pH, totalcarbon and alkalinity in seawater.
    Type of Medium: Electronic Resource
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