Chemical Thermodynamics of Tin - Volume 12 - OECD Nuclear ...

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406 A Discussion of selected references [1995DJU/JEL] The hydrolysis of tin(II) ion has been studied in 3.0 M (Na)Cl medium at 298 K, by potentiometric titrations using a glass electrode. In the concentration range 2 1.0 ≤ c(Sn + + ο ) /mM ≤ 10.0 and 0.50 ≤ − log 10 [ c(H ) / c ] ≤ 1.30, the experimental data were explained by the formation of the following complexes and their respective 2 stability constants, ( log10 β pq , ± σ): Sn 3(OH) + 4 , − (2.70 ± 0.01) and SnOH + , − (2.18 ± 0.02). These constants are much higher than those reported in 3 M NaClO 4 (see comment on [1958TOB]), indicating that the hydrolytic processes strongly shifted 2−q toward the acidic region. Since the formation of SnClq complexes should retard the hydrolysis, the authors tried to explain this inconsistency by the highly asymmetric distribution of the electron density of the hybridised 5s orbital of tin(II), and by the role of chloride ion which “may aid in oxygen bonding to the tin by their electrostatic influence on H–OH bonds”. Although these speculations may be true (moreover the formation of the mixed hydroxido complex Sn(OH)Cl(aq) may result in a similar pH 2−q shift), the formation of SnClq complexes were not taken into account during the evaluation of experimental data, therefore the reported formation constants are not considered further in this review. From the experimental point of view the correct determination of hydrogen ion concentration between pH = 0.5 and 1.3 is doubtful using a glass electrode, and the experimental errors generated in this way may also explain the above mentioned inconsistency. In addition, the solubility product of Sn(OH) 2 (s) was determined from the + hydrolytic curves, Z (− log 10 c(H )) and found to be, pK s = (27.9 ± 0.1). The hydrolytic precipitate was examined by elemental analysis, thermogravimetry, IR spectroscopy, X- ray powder diffraction and scanning electron microscopy. It was presumed that the main constituent of the precipitate can be formulated as SnO·H 2 O. This paper is particularly interesting, because the hydrolytic precipitate, presumably SnO·H 2 O, was characterised structurally. Comparison of the X-ray powder patterns, reported by the authors, with PDF files 01-084-2157 and 01-077-0452 of JCPDS indicates that the main constituent of the hydrolytic precipitate was Sn 6 (OH) 4 O 4 , hydroromarchite, but probably a minor amount of SnO 2 , cassiterite, was also present, see Table A-68. A recalculation shows that the solubility data of [1995DJU/JEL] neither agree with those predicted for abhurite, Sn 21 Cl 16 (OH) 14 O 6 , nor with those predicted for SnO, romarchite, see Figure A-47. By massive parallel displacement the experimental data coincide rather with the SnO solubility curve than with the abhurite one. This confirms the authors’ implication that the hydrolytic precipitate contains no chloride. The low solubility of the hydrolytic precipitate may be related to its SnO 2 , cassiterite, content, but no thermodynamic data can be derived. CHEMICAL THERMODYNAMICS OF TIN, ISBN 978-92-64-99206-1, © OECD 2012
A Discussion of selected references 407 Table A-68: Comparison of X-ray powder diffraction patterns with JCPDS. SnO·H 2 O d/Ǻ [1995DJU/JEL] i Sn 6 O 4 (OH) 4 d/Ǻ 01-084-2157 i SnO 2 d/Ǻ 01-077-0452 i 6.004 vw 5.97784 444 5.624 vw 5.60509 381 4.554 vw 4.55125 170 3.533 w 3.53318 999 3.379 w 3.36243 999 3.316 w 3.30330 594 3.246 w 2.986 w 2.98892 775 2.810 s 2.79671 862 2.621 w 2.65438 757 2.495 w 2.50667 368 1.981 m 1.97963 24 Figure A-47: Sn(OH) 2 solubility in 3.0 M NaCl (: Experimental data of [1995DJU/JEL]; : parallel displaced data (x + 2.65, y + 11); solid line: calculated solubility of abhurite; dashed line: calculated solubility of SnO(cr)). -0.5 -1.0 log 10 (m Sn(II) / mol·kg –1 ) -1.5 -2.0 -2.5 -3.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 – log 10 (m H + / mol·kg –1 ) CHEMICAL THERMODYNAMICS OF TIN, ISBN 978-92-64-99206-1, © OECD 2012
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CHEMICAL THERMODYNAMICS OF TIN Hein
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CHEMICAL THERMODYNAMICS Vol. 1. Che
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vi Preface of the successive drafts
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viii Acknowledgements for peer revi
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x How to contact the NEA TDB Projec
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xii Contents III Selected tin data
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xiv Contents VIII.3 Aqueous halide
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xvi Contents B.1.3.2 Estimations ba
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xviii List of figures Figure VII-12
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xx List of figures Figure IX-3: Hea
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xxii List of figures Figure A-35: S
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List of tables Table II-1: Abbrevia
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List of tables xxvii Table VIII-1:
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List of tables xxix Table IX-4: Tab
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List of tables xxxi Table A-21: Sta
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List of tables xxxiii Table A-64: T
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Part 1 Introductory material
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4 I Introduction and Ti. In 1976, t
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6 I Introduction The present review
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8 I Introduction subjective choice
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10 II Standards, conventions and co
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30 II.3 II Standards, conventions a
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Part 2 Tables of selected data
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44 III Selected tin data Table III-
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50 III Selected tin data Species Re
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Chapter IV Selected auxiliary data
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IV Selected auxiliary data 57 Table
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IV Selected auxiliary data 75 Speci
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IV Selected auxiliary data 77 Speci
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Part 3 Discussion of data selection
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82 V Elemental tin transition, call
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84 V Elemental tin ο Table V-3: Co
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86 V Elemental tin Table V-6: Param
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Chapter VI VI Simple tin aqua ionsE
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VI.2 Sn 2+ 91 at 24.5 °C in aqueou
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VI.2 Sn 2+ 93 Reference Table VI-1:
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VI.2 Sn 2+ 95 As only three data pa
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VI.2 Sn 2+ 97 Figures A-37 to A-40.
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VI.3 Sn 4+ 99 Sn 4+ + H 2 (g) Sn 2
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VI.3 Sn 4+ 101 (NH 4 ) 2 SnCl 6 see
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VI.3 Sn 4+ 103 Sn 4+ + H 2 (g) Sn
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VI.3 Sn 4+ 105 Figure VI-3: Modifie
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108 VII Tin oxygen and hydrogen com
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138 VIII Group 17 (halogen) compoun
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Chapter IX IX Group 16 compounds an
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IX.1 Sulfur compounds and complexes
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232 X Group 15 compounds and comple
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Chapter XI XI Group 14 compounds an
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XI-1 Aqueous tin thiocyanato comple
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Appendix A Discussion of selected r
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A Discussion of selected references
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Page 391 and 392: A Discussion of selected references
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Page 471 and 472: B Appendix B Ionic strength correct
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B.3 4BTables of ion interaction coe
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484 C Assigned uncertainties The mi
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486 C Assigned uncertainties discus
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488 C Assigned uncertainties In cas
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490 C Assigned uncertainties The un
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492 C Assigned uncertainties In thi
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494 C Assigned uncertainties bit fu
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496 C Assigned uncertainties that t
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498 C Assigned uncertainties Eq. (C
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Bibliography [1813BER] [1831NEU] [1
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