Hydrolysis and chemical speciation of dioxouranium(VI) ion in aqueous media simulating the major ion composition of seawater

Antonio Gianguzza, Demetrio Milea, Frank J. Millero, Silvio Sammartano

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37 Scopus citations


The hydrolysis and chemical speciation of the dioxouranium(VI) ion at 25°C was studied in a number of binary electrolytes (LiCl, NaCl, MgCl 2, CaCl2, Na2SO4) and some mixtures (NaCl-Na2SO4, NaNO3-Na2SO 4, CaCl2-MgCl2) as well as artificial seawater (SSWE) as a function of ionic strength. The results in LiCl, CaCl2 and MgCl2 solutions confirmed the formation of (UO2) 2(OH)22+, (UO2)3(OH) 42+, (UO2)3(OH)5 + and (UO2)3(OH)7- species (at I=0 mol l-1: log Tβ22=-5.76, log Tβ34=-11.82, log Tβ 35=-15.89 and log Tβ37=-29.26). For NaNO3, NaCl and artificial seawater the hydrolysis constant for the formation of the UO2(OH)+ species was also determined (at I=0 mol l-1: log Tβ11=-5.19). The results in Na2SO4, Na2SO4/NaNO3 and Na2SO4/NaCl required the formation of UO 2(SO4)0, UO2(SO4) 22-, UO2(OH)SO4-, (UO2)2(OH)2SO40, (UO 2)3(OH)4SO40 and (UO 2)3(OH)5SO4-, whose estimated values of each complex formation constant at I=0 mol (kg H 2O)-1 are (log Tβ pqr±standard deviation, species in parenthesis): 3.32±0.02 [UO2SO40], 4.26±0.04 [UO 2(SO4)22-], -2.30±0.01 [UO2(OH)(SO4)-], -2.64±0.04 [(UO 2)2(OH)2(SO4)0], -8.45±0.04 [(UO2)3(OH)4(SO 4)0], -13.58±0.04 [(UO2) 3(OH)5(SO4)-]. All the results were examined using the Pitzer model by considering the interactions of the cation hydrolytic species with Cl- and NO3- and anion hydrolytic species with Li+, Na+, Ca2+ and Mg2+ and, in addition, the "same sign" and "triple" interaction parameters. The resulting Pitzer parameters give an adequate representation of all the hydrolysis constants measured in the binary, ternary and artificial seawater solutions. Alternatively to the interpretation of the dependence of uranyl hydrolysis constants on ionic strength and on ionic medium in terms of variations of activity coefficients of ions, the formation of ion pairs was considered and some complex formation constants among dioxouranium(VI) species and different ions of background salts were calculated. Interactions of uranyl with major components of seawater were taken into account using the "single salt" BA approximation according to which SSWE is considered as a single sea salt (BA) where cation B and anion A, having charge z=±√/CBA=±1.117, are representative of all major cations (Na+, K+, Ca 2+, Mg2+) and anions (Cl- and SO 42-) of seawater, respectively. Pitzer parameters were also calculated for both the interactions of uranyl with Bz+ and Az- ions and for the internal BA interactions. The last ones are: β(0)=0.1081 and β(1)=0.4238 for B 1.117+-A1.117- interactions, and β (0)=-0.3134 and β(1)=1.5375 for H+-A 1.117- interactions. Literature data were collected carefully, and a critical analysis and accurate comparisons with results presented here were made.

Original languageEnglish (US)
Pages (from-to)103-124
Number of pages22
JournalMarine Chemistry
Issue number3-4
StatePublished - Mar 2004


  • Chemical speciation
  • Dependence on ionic medium
  • Dependence on ionic strength
  • Dioxouranium(VI)
  • Hydrolysis
  • Ion pair formation
  • Pitzer parameters
  • Seawater

ASJC Scopus subject areas

  • Oceanography
  • Chemistry(all)
  • Environmental Chemistry
  • Water Science and Technology


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