Hydrolysis of Monomethyl-, Dimethyl-, and Trimethyltin(IV) Cations in Fairly Concentrated Aqueous Solutions at I = 1 mol L-1 (NaNO3) and T = 298.15 K. Evidence for the Predominance of Polynuclear Species

Antonio Gianguzza, Alba Giacalone, Silvio Sammartano, Concetta De Stefano, Rosalia M. Cigala

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Abstract

The hydrolysis of methyltin(IV) cations at fairly high concentrations was investigated to evaluate the formation of polynuclear species in aqueous solution. The hydrolysis of monomethyltin(IV), dimethyltin(IV), and trimethyltin(IV) was studied by potentiometry at T = 298.15 K and at I = 1 mol L-1 in NaNO3 aqueous solutions. The results obtained gave evidence for the formation of the following polynuclear species, in addition to the mononuclear species already reported, which were also considered in the models proposed for the three systems investigated: [(CH3)Sn(OH)3]0, [(CH3)Sn(OH)4]-, [((CH3)Sn)2(OH)4]2+, [((CH3)Sn)2(OH)5]+, [((CH3)Sn)2(OH)7]-, [((CH3)Sn)3(OH)5]4+, [((CH3)Sn)3(OH)7]2þ, [((CH3)Sn)5(OH)9]6þ, and [((CH3)Sn)5(OH)11]4þ for the monomethyltin(IV) system; [((CH3)2Sn)(OH)]þ, [((CH3)2Sn)(OH)2]0, [((CH3)2Sn)(OH)3]-, [((CH3)2Sn)2(OH)2]2+, [((CH3)2Sn)2(OH)3]+, [((CH3)2Sn)3(OH)4]2+, and [((CH3)2Sn)4(OH)6]2+ for the dimethyltin(IV) system; [((CH3)3Sn)(OH)]0, [((CH3)3Sn)(OH)2]-, [((CH3)3Sn)2(OH)]+, [((CH3)3Sn)2(OH)2]0, and [((CH3)3Sn)2(OH)4]2- for the trimethyltin(IV) system. The formation constants βpqOH (relative to the equilibrium p(CH3)nSn(4-n)+ + qOH- = ((CH3)nSn)p(OH)q(p(4-n)-q)) can be expressed as a function of the cation charge z (z = 4-n) by the general equation: log βpqOH / (p+q) = 1 + (2.50 ± 0.05)z, that allows the calculation of rough values of βpqOH for any (p,q) couple. The reliability of the proposed speciation models is discussed. As expected for a tricharged cation, by increasing the concentration of (CH3)Sn3+, the yield of polynuclear species becomes predominant; this behavior is less marked for (CH3)2Sn2+ and (CH3)3Sn+.
Lingua originaleEnglish
pagine (da-a)1108-1115
Numero di pagine8
RivistaJournal of Chemical and Engineering Data
Volume56
Stato di pubblicazionePublished - 2011

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Cations
Hydrolysis
Positive ions
trimethyltin
dimethyltin
methyltin

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

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@article{59116736e0f44879a22bf5899f688ab3,
title = "Hydrolysis of Monomethyl-, Dimethyl-, and Trimethyltin(IV) Cations in Fairly Concentrated Aqueous Solutions at I = 1 mol L-1 (NaNO3) and T = 298.15 K. Evidence for the Predominance of Polynuclear Species",
abstract = "The hydrolysis of methyltin(IV) cations at fairly high concentrations was investigated to evaluate the formation of polynuclear species in aqueous solution. The hydrolysis of monomethyltin(IV), dimethyltin(IV), and trimethyltin(IV) was studied by potentiometry at T = 298.15 K and at I = 1 mol L-1 in NaNO3 aqueous solutions. The results obtained gave evidence for the formation of the following polynuclear species, in addition to the mononuclear species already reported, which were also considered in the models proposed for the three systems investigated: [(CH3)Sn(OH)3]0, [(CH3)Sn(OH)4]-, [((CH3)Sn)2(OH)4]2+, [((CH3)Sn)2(OH)5]+, [((CH3)Sn)2(OH)7]-, [((CH3)Sn)3(OH)5]4+, [((CH3)Sn)3(OH)7]2{\th}, [((CH3)Sn)5(OH)9]6{\th}, and [((CH3)Sn)5(OH)11]4{\th} for the monomethyltin(IV) system; [((CH3)2Sn)(OH)]{\th}, [((CH3)2Sn)(OH)2]0, [((CH3)2Sn)(OH)3]-, [((CH3)2Sn)2(OH)2]2+, [((CH3)2Sn)2(OH)3]+, [((CH3)2Sn)3(OH)4]2+, and [((CH3)2Sn)4(OH)6]2+ for the dimethyltin(IV) system; [((CH3)3Sn)(OH)]0, [((CH3)3Sn)(OH)2]-, [((CH3)3Sn)2(OH)]+, [((CH3)3Sn)2(OH)2]0, and [((CH3)3Sn)2(OH)4]2- for the trimethyltin(IV) system. The formation constants βpqOH (relative to the equilibrium p(CH3)nSn(4-n)+ + qOH- = ((CH3)nSn)p(OH)q(p(4-n)-q)) can be expressed as a function of the cation charge z (z = 4-n) by the general equation: log βpqOH / (p+q) = 1 + (2.50 ± 0.05)z, that allows the calculation of rough values of βpqOH for any (p,q) couple. The reliability of the proposed speciation models is discussed. As expected for a tricharged cation, by increasing the concentration of (CH3)Sn3+, the yield of polynuclear species becomes predominant; this behavior is less marked for (CH3)2Sn2+ and (CH3)3Sn+.",
keywords = "speciation, organotin hydrolysis, polynuclear species",
author = "Antonio Gianguzza and Alba Giacalone and Silvio Sammartano and {De Stefano}, Concetta and Cigala, {Rosalia M.}",
year = "2011",
language = "English",
volume = "56",
pages = "1108--1115",
journal = "Journal of Chemical & Engineering Data",
issn = "0021-9568",
publisher = "American Chemical Society",

}

TY - JOUR

T1 - Hydrolysis of Monomethyl-, Dimethyl-, and Trimethyltin(IV) Cations in Fairly Concentrated Aqueous Solutions at I = 1 mol L-1 (NaNO3) and T = 298.15 K. Evidence for the Predominance of Polynuclear Species

AU - Gianguzza, Antonio

AU - Giacalone, Alba

AU - Sammartano, Silvio

AU - De Stefano, Concetta

AU - Cigala, Rosalia M.

PY - 2011

Y1 - 2011

N2 - The hydrolysis of methyltin(IV) cations at fairly high concentrations was investigated to evaluate the formation of polynuclear species in aqueous solution. The hydrolysis of monomethyltin(IV), dimethyltin(IV), and trimethyltin(IV) was studied by potentiometry at T = 298.15 K and at I = 1 mol L-1 in NaNO3 aqueous solutions. The results obtained gave evidence for the formation of the following polynuclear species, in addition to the mononuclear species already reported, which were also considered in the models proposed for the three systems investigated: [(CH3)Sn(OH)3]0, [(CH3)Sn(OH)4]-, [((CH3)Sn)2(OH)4]2+, [((CH3)Sn)2(OH)5]+, [((CH3)Sn)2(OH)7]-, [((CH3)Sn)3(OH)5]4+, [((CH3)Sn)3(OH)7]2þ, [((CH3)Sn)5(OH)9]6þ, and [((CH3)Sn)5(OH)11]4þ for the monomethyltin(IV) system; [((CH3)2Sn)(OH)]þ, [((CH3)2Sn)(OH)2]0, [((CH3)2Sn)(OH)3]-, [((CH3)2Sn)2(OH)2]2+, [((CH3)2Sn)2(OH)3]+, [((CH3)2Sn)3(OH)4]2+, and [((CH3)2Sn)4(OH)6]2+ for the dimethyltin(IV) system; [((CH3)3Sn)(OH)]0, [((CH3)3Sn)(OH)2]-, [((CH3)3Sn)2(OH)]+, [((CH3)3Sn)2(OH)2]0, and [((CH3)3Sn)2(OH)4]2- for the trimethyltin(IV) system. The formation constants βpqOH (relative to the equilibrium p(CH3)nSn(4-n)+ + qOH- = ((CH3)nSn)p(OH)q(p(4-n)-q)) can be expressed as a function of the cation charge z (z = 4-n) by the general equation: log βpqOH / (p+q) = 1 + (2.50 ± 0.05)z, that allows the calculation of rough values of βpqOH for any (p,q) couple. The reliability of the proposed speciation models is discussed. As expected for a tricharged cation, by increasing the concentration of (CH3)Sn3+, the yield of polynuclear species becomes predominant; this behavior is less marked for (CH3)2Sn2+ and (CH3)3Sn+.

AB - The hydrolysis of methyltin(IV) cations at fairly high concentrations was investigated to evaluate the formation of polynuclear species in aqueous solution. The hydrolysis of monomethyltin(IV), dimethyltin(IV), and trimethyltin(IV) was studied by potentiometry at T = 298.15 K and at I = 1 mol L-1 in NaNO3 aqueous solutions. The results obtained gave evidence for the formation of the following polynuclear species, in addition to the mononuclear species already reported, which were also considered in the models proposed for the three systems investigated: [(CH3)Sn(OH)3]0, [(CH3)Sn(OH)4]-, [((CH3)Sn)2(OH)4]2+, [((CH3)Sn)2(OH)5]+, [((CH3)Sn)2(OH)7]-, [((CH3)Sn)3(OH)5]4+, [((CH3)Sn)3(OH)7]2þ, [((CH3)Sn)5(OH)9]6þ, and [((CH3)Sn)5(OH)11]4þ for the monomethyltin(IV) system; [((CH3)2Sn)(OH)]þ, [((CH3)2Sn)(OH)2]0, [((CH3)2Sn)(OH)3]-, [((CH3)2Sn)2(OH)2]2+, [((CH3)2Sn)2(OH)3]+, [((CH3)2Sn)3(OH)4]2+, and [((CH3)2Sn)4(OH)6]2+ for the dimethyltin(IV) system; [((CH3)3Sn)(OH)]0, [((CH3)3Sn)(OH)2]-, [((CH3)3Sn)2(OH)]+, [((CH3)3Sn)2(OH)2]0, and [((CH3)3Sn)2(OH)4]2- for the trimethyltin(IV) system. The formation constants βpqOH (relative to the equilibrium p(CH3)nSn(4-n)+ + qOH- = ((CH3)nSn)p(OH)q(p(4-n)-q)) can be expressed as a function of the cation charge z (z = 4-n) by the general equation: log βpqOH / (p+q) = 1 + (2.50 ± 0.05)z, that allows the calculation of rough values of βpqOH for any (p,q) couple. The reliability of the proposed speciation models is discussed. As expected for a tricharged cation, by increasing the concentration of (CH3)Sn3+, the yield of polynuclear species becomes predominant; this behavior is less marked for (CH3)2Sn2+ and (CH3)3Sn+.

KW - speciation, organotin hydrolysis, polynuclear species

UR - http://hdl.handle.net/10447/54203

M3 - Article

VL - 56

SP - 1108

EP - 1115

JO - Journal of Chemical & Engineering Data

JF - Journal of Chemical & Engineering Data

SN - 0021-9568

ER -