Separation of methyltin species from inorganic tin,and their interactions with humates in natural waters

Tin(II) and tin(IV) are absorbed from aqueous solutions by Sephadex G-25 gel, from which they can be eluted by humates or fulvates, with which they interact more strongly. Methyltin species are not absorbed by Sephadex G-25, and so can be separated from inorganic tin. Both inorganic tin and methyltin species in natural waters at pH 7.4 can be quantitatively retained by passing through small columns of Chelex-100 resin: the methyltin species can then be washed off the resin with 4M nitric acid. Trimethyltin chloride¹¹³Sn in water scarcely interacts with fulvates, humates, kaolinite or montmorillonite but is absorbed bySphagnum peat. Dimethyltin dichloride-¹¹³Sn reacts significantly with all the above materials after 2 hours equilibration. Methyltin trichloride-¹¹³Sn interacts weakly in alkaline solutions.     

Separation of tin from some metals by extraction chromatography

Much attention has been devoted to Sn (IV) strongly retained on the TBP-Daiflon column from 2M HCl in extraction chromatography. The separations of Sn?Cu, Zn, As, Cd, Sb, Pb,¹¹³Sn-¹²⁵Sb,¹¹³Sn-^113mIn (^113mIn milking) and Sn?Hg?Fe were successfully achieved without any contamination. In the separations, except for the last, only tin was retained separately on the column upon passing the mixed solution. The daughter indium was eluted with 0.5M HCl. In the last separation, iron was eluted with 0.5 M HCl, tin with 0.1M HCl and mercury with 2M HNO₃, for these metals retained on the column. Radioactive tracers for tin, iron, mercury and antimony were used.     

Extraction of Ag(I), Cd(II), In(III), Sn(II), Sn(IV), Sb(III), and U(VI) from aqueous solutions by ketone solutions using single-step batch and continuous SISAK methods1,2

The extraction properties of Ag(I), Cd(II), In(III), Sn(II), Sn(IV), Sb(III), and U(VI) from aqueous KI/H₂SO₄ solution into a mixture of 4-methyl-2-pentanone (methyl isobutyl ketone, MIBK) and cyclohexanone (CHO) were studied. Both single-step batch and SISAK² methods were used. The oxidation of Sn(II) to Sn(IV) by iodine and complexation of Sn(IV) by 2,3-dimercapto-propanol-1 (BAL) were also investigated. A method for rapid and continuous separation of indium from tin was developed for investigation of short-lived indium fission products.     

Preparation and reflow soldering characteristics of solder paste containing submicron Sn powders synthesised via chemical reduction

Sn nanoparticles (NPs) were synthesised via chemical reduction. Trisodium citrate dihydrate and mixtures of trisodium citrate dihydrate and 1,10-phenanthroline monohydrate were used as capping agents for the synthesis. When a specific amount of trisodium citrate dihydrate (3.4 × 10^?1 mM) was solely added, very fine particle sizes and excellent suppression of aggregation were achieved in the dried samples. When 5 mM of 1,10-phenanthroline monohydrate was used in combination with trisodium citrate dihydrate (at the optimum concentration of 3.4 × 10^?2 mM), the particle refining and the suppression of aggregation were further improved. The nano-solder paste prepared by mixing the synthesised Sn NPs with a commercial flux exhibited stable reflow soldering characteristics. The formation of an intermetallic layer, similar to that observed when commercial solder pastes containing micron-sized powders were used, was seen when soldering was carried out with the solder paste containing the synthesised Sn NPs.     

The determination of tin in rocks by thermal neutron activation

A fast routine method for the determination of tin in rocks is discussed. The method is based on coprecipitation of tetravalent tin with ferric hydroxide, followed by a short irradiation in a high thermal neutron flux, extraction in toluene from 1∶1 sulphuric acid which is 5N in potassium iodide, and counting of^123mSn (T=40 m) or^125mSn (T=9.7 m) with a well-type NaI detector. In the present work^125mSn was used. The lower limit of determination is governed by the blank of the reagents. For a sample of at least one gram it is ≌ 0.2 μg Sn·g⁻¹.     

Fast determination of the tin content in cassiterite ores by photon activation method

Photon activation analysis has been success-fully applied to the fast and non-destructive analysis of tin in cassiterite ores based on the 159.7 keV gamma line of^123mSn produced in the¹²⁴Sn/γ, n/^123mSn reaction. In order to improve the accuracy of analytical results, corrections for self-absorption and pile-up effects were performed. Under typical conditions /15 μA electron beam current, 15 MeV bremsstrahlung energy, 5 min irradiation time and 10 min measurement/ the sensitivity of the analysis is 10 ppm. The proposed method can be used for routine analysis of tin in geological samples.     

Interferences in the determination of trace elements in high-purity tin

Reactor neutron activation analysis of antimony, indium and cadmium in high-purity tin is interfered with by nuclear reactions on the tin matrix. For a number of interfering reactions the cross-sections were determined. The following results were obtained:¹²²Sn(n,γ)^123mSn:σ_th=0.145 barn, I=0.79 barn;¹²²Sn(n,γ)¹¹³Sn:σ_th=0.52, I=25.4 barn;¹¹²Sn(n, 2n)¹¹¹Sn: microbarn;¹¹⁸Sn(n, α)¹¹⁵Cd: microbarn; and¹¹⁴Sn(n, p)^114m1In: microbarn.     

A radiochemical neutron activation analysis method for the determination of tin,arsenic, copper and antimony for the forensic comparison of bullet lead specimens

Trace element characterization of bullet lead by instrumental neutron activation analysis (INAA) is hampered by the high spectral background due to antimony, normally present in high concentration in bullet lead. Tin is indicated to be a very useful element for characterization purposes. Beta-active¹²¹Sn is a suitable nuclide for quantitation of tin provided it is separated in high radiochemical purity. A radiochemical procedure capable of determining tin down to 10 ppm in bullet lead, a sequential procedure for its determination along with copper, arsenic and antimony and the application of this procedure for the determination of the contents of these elements in various bullet leads are described. This method has been applied to a “Rhinoceros shoot-out” case, referred to our laboratory.     

Simplified synthesis, H, C, N, Sn NMR spectra and X-ray structures of diorganotin(IV) complexes containing the 4-phenyl-2,4-butanedionebenzoylhydrazone(2−) ligand

Two diorganotin(IV) complexes of the general formula R₂Sn[Ph(O)CCH-C(Me)N-NC(O)Ph] (R=Ph, 1; R=Me, 2) have been synthesised from the corresponding diorganotin(IV) dichloride and the ligand 4-phenyl-2,4-butanedionebenzoylhydrazone(2−) (H₂L), derived from benzoyl acetone and benzoyl hydrazide in methanol at room temperature in presence of triethylamine. The syntheses were performed under very mild conditions, at room temperature and without exclusion of air or moisture from the reaction vessel. Previously, rigorous conditions have been considered necessary for these species. The two compounds have been characterised by elemental analysis, IR and ¹H, ¹³C, ¹⁵N, ¹¹⁹Sn NMR spectra, and their structures have been confirmed single crystal X-ray structure analysis. The central tin atom of both complexes adopts a distorted trigonal bipyramidal coordination with two ligand oxygen atoms in axial positions, the nitrogen atom of the ligand and two organic groups on tin occupying equatorial sites. 2 has crystallised with two crystallographically independent molecules in the asymmetric unit. The δ(¹¹⁹Sn) values for the complexes 1 and 2 are −151.5 and −146.8 ppm, respectively, thus indicating penta-coordinated tin centres.     

The Effect of O6+ and Si7+ ion beam irradiations on poly(lactide-co-glycolide) (50: 50) copolymer

Sterilization by ion beam radiations unfortunately also has a significant effect on the degradation of many polymers. The aim of present study is to examine the effect of heavy ion beam irradiation on poly(lactide-co-glycolide) (PLGA) (50: 50). The radiation effect is manifested through its degradation behavior and changes in the morphological, optical and structural properties. PLGA films are prepared by solvent casting method and subsequently irradiated with swift heavy ions O⁶⁺ and Si⁷⁺ ion with fluence in the range of 5 × 10¹⁰?1 × 10¹² ions/cm². The dominant effect on PLGA films is chain scission as evidenced by change in surface modification. Changes in optical and structural properties were analyzed by UV-Vis, XRD and FTIR spectrometric techniques. XRD technique is not responsive to degradation occurring in samples. Surface modifications caused by ion irradiations have been observed with SEM.     

Lithiumtriamidostannat(II), Li[Sn(NH2)3] – Synthese und Kristallstruktur

Lithium Triamidostannate(II), Li[Sn(NH₂)₃] – Synthesis and Crystal Structure Rusty-red glistening, transparent crystals of Li[Sn(NH₂)₃] were obtained by reaction of metallic lithium with tetraphenyl tin in liquid ammonia at 110 °C. The structure was determined from X-ray single-crystal diffractometer data: Space group P 2₁/n, Z = 4, a = 8.0419(9) Å, b = 7.1718(8) Å, c = 8.5085(7) Å, β = 90.763(8)°, R₁ (F _o ≥ 4σ(F _o)) = 2.8%, wR₂ (F ≥ 2σ(F )) = 5.3%, N(F ≥ 2σ(F )) = 1932, N(Var.) = 65. The crystal structure contains trigonal pyramidal complex anions [Sn(NH₂)₃]^– with tin at the apex, which are connected to layers of sequence A B A B … by lithium in tetrahedra-double units [Li(NH₂)_2/2(NH₂)₂]₂.     

Modification of a Pt surface by spontaneous Sn deposition for electrocatalytic applications

In the present communication we explored a simple dip-coating method for spontaneous (without applying an external current or additional reducing agents) modification of Pt surface by both tin oxy-species and tin metal based on hydrolysis of tin chloride complex and autocatalytic (electroless) deposition of tin for fabrication of the fuel cell catalysts with improved CO tolerance. It consisted of (i) Pt immersion into SnCl₂/HCl solution under open-circuit conditions; (ii) subsequent rinsing of the surface by pure water. The resulting Sn-modified Pt surfaces were characterized by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). Two types of tin species, namely, tin oxide/hydroxide species and metallic tin were identified at Pt surface. Tin oxide/hydroxide species were assumed to be derived as a result of Sn(II) chloride complex hydrolysis, while tin metal particles were most likely deposited spontaneously on Pt surface due to disproportionation of Sn(II) to Sn(IV) and metallic tin, competing with dissolution of the Sn deposit in strongly acidic medium. Modifying tin species show a satisfactory stability in 0.5-M H₂SO₄ solution at potentials relevant to low-temperature fuel cell operating conditions (below 0.6 V vs. a standard hydrogen electrode, SHE).     

Electron spectroscopic investigation of Sn coatings on glasses

Float glasses of different thicknesses and a conducting tin oxide glass have been investigated using Photo and Auger Electron Spectroscopy induced by AlK X-rays. On the basis of measured chemical XPS shifts in the binding energies the chemical state of Sn (+2 or +4) incorporated on the float glasses could not be assigned. The use of the Auger parameter allows to separate relaxation and chemical contributions. The derived true chemical shifts of Sn on float-glasses are larger than those of SnO and/or SnO₂ due to the larger ionic environment of the glass matrix. Ar⁺ or HF etching reveals that the concentration of Sn decreases exponentially as a function of depth from the surface.     

Mössbauer study of some ion-beam irradiated Co−Sn electrodeposits

The effect of ion-beam irradiation on the composition and structure of some Co–Sn electrodeposits has been studied by Mössbauer spectroscopy. A transformation of dissolved tin and cubic CoSn to -Co₃Sn₂ was observed.     

Neutral Hexacoordinate Tin(IV) Halide Complexes with 4,4'-Dimethy-2,2'-bipyridine

A series of three neutral, hexacoordinate tin(IV) complexes were synthesized by the reaction of 4,4'-dimethyl-2,2'-bipyridine (DMB) with SnX₄, X = Cl, Br, and I, as starting materials. The complexes (DMB)SnX₄ were characterized in solution by ¹H, ¹³C, and ¹¹⁹Sn NMR spectroscopy, and in the solid-state by ¹¹⁹Sn MAS NMR spectroscopy. In addition, single-crystal X-ray diffraction and elemental analysis were used to confirm the molecular structures. In these complexes, the tin atom adopts a distorted octahedral arrangement and the DMB acts as a bidentate N,N'-chelate ligand. Computational DFT methods were also employed to gain more insight into the nature of the bonding in these complexes, including the hypothetical complexes (DMB)SnX₄ (X = F, At). Additionally, the validity and reliability of the ¹¹⁹Sn NMR chemical shifts were examined. The calculated values were compared with the experimental signals and the effects of structure and solvent are discussed. Finally, all of the complexes (DMB)SnX₄ were successfully tested for the ring-opening polymerization (ROP) of bulk ε-caprolactone under non-dried and aerobic conditions as precatalyst.     

N → Sn coordination in the complexes of tin halides with pyridine: A comparison between Sn(II) and Sn(IV)

The experimentally well‐known complexation of tin(II) and tin(IV) halides with pyridine (py) leads to structures showing N → Sn coordination. In the present work, the complexes SnX_n·mpy (where X = F, Cl, Br, I; n = 2, 4; m = 1, 2) possessing this kind of coordination were studied using a computational quantum chemical approach. Various aspects in the theoretical picture of these complexes were examined to find similarities and differences in their N → Sn coordination. The aspects included, among others, the physical nature of intermolecular interactions, and their role in establishing the structure and energetic stabilization of the complexes. In this context, the effect of tin valency was inspected in great detail. As proven by several theoretical methods, a largely ionic character with a certain covalent component can be attributed to the studied N → Sn coordination, irrespective of tin valency. All complexes are destabilized by py‐py and three‐body interactions, but the Sn(II) complexes experience it to a greater extent. Marked differences are observed in the structural behavior of N → Sn and SnX_n during complex formation. This affects the energetics of complexation and, in consequence, the penta‐coordinated Sn(IV) center shows a higher propensity to expand its coordination number, compared with the tri‐coordinated Sn(II) center. The present study supplements the experimental characterization of SnX_n·mpy and, in general, it sheds light on the coordination of heteroaromatic nitrogen to tin. The survey of the Cambridge Structural Database revealed that such coordination occurred in a number of crystal structures.     

The reaction of diphenyltin (IV) or triphenyltin (IV) chloride with 3,4,5-trimethoxybenzoyl salicylahydrazone. The crystal structure of Ph2[(MeO)3C6H2C(O)N2CHC6H4O]Sn

The title complex has been synthesized by the reaction of diphenyltin(IV) or triphenyltin(IV) chloride with 3,4,5-trimethoxybenzoyl salicylahydrazone and characterized by ¹H, ¹³C, ¹¹⁹Sn NMR, and IR spectral studies. An X-ray analysis shows that the ligand is tridentate and approximately planar and the central tin atom is in a distorted five-coordinate trigonal bipyramidal geometry. The complex crystallizes in the monoclinic space group C2/c with a = 29.194(4), b = 10.117(1), c = 22.524(3) Å, β = 124.44(2)°, V = 5486.5(8) ų, Z = 8. The Sn C bond lengths are 2.123(9) and 2.116(7) Å, and the bond length between the tin atom and the coordinating nitrogen atom (Sn–N bond) is 2.152(6) Å. The C Sn C bond angle and the bond angle between the tin atom and the two axially positioned oxygen atoms are 129.1(1) and 156.17(9)°, respectively. The structure was refined to final R = 0.056 and R_w = 0.074 for 4145 observed reflections with I > 3σ(I). © John Wiley & Sons, Inc.     

Evaluation of natural gamma radiation and absorbed gamma dose in soil and rocks of Perambalur district (Tamil Nadu,India)

The activity concentrations and absorbed gamma dose of primordial radionuclides ²³⁸U, ²³²Th and ⁴⁰K were determined employing γ-ray spectrometry in 31 soil samples from the land area earmarked for house construction in Perambalur district and 14 rock samples from quarries that supply stones for the entire district. The soil samples registered relatively a higher mean value of 13.2 Bq kg^?1 for ²³⁸U, 66 Bq kg^?1 for ²³²Th and 340.3 Bq kg^?1 for ⁴⁰K as compared to mean values for rock samples (²³⁸U—8.0 Bq kg^?1; ²³²Th—65.1 Bq kg^?1; ⁴⁰K—199.1 Bq kg^?1). The mean absorbed gamma dose rate for soil (61.4 nGy h^?1) marginally exceeded the prescribed limit of 55 nGy h^?1 while, rocks registered the mean absorbed gamma dose rate of 10.4 nGy h^?1. The mean radium equivalent activity was distinctly higher in soil (130.6 Bq kg^?1) than in rock (20.0 Bq kg^?1). However, these values were lower than the limit (370 Bq kg^?1) set by OECD for building materials. It is evident from the data that the soil and rocks do not pose any radiological risk for house constructions in Perambalur district.     

Study by grazing incident diffraction and surface spectroscopy of amalgams from ancient mirrors

Characterization of four amalgam surfaces, with different alteration degrees from Andalusia historical mirrors, has been carried out by grazing-incidence X-ray diffraction (GIXRD), and other spectroscopic techniques (SEM/EDX, XPS, and REELS). The combination of all these techniques allows determining the corrosion state of the amalgams. The results show that the amalgams are composed in all cases of a binary alloy of tin and mercury. As mercury has high vapour pressure at RT, it slowly segregates and eventually evaporates, it leaves finely divided particles of tin that easily can be oxidize, forming tin monoxide (SnO) and tin dioxide (SnO₂). In one of the samples, most of the amalgam remains unoxidized, since Hg_0.1Sn_0.9 and metallic Sn phases are the major components; in two other samples, Hg_0.1Sn_0.9 and Sn phases are not detected while SnO₂ and SnO phases appear. Finally, in the last studied sample, only SnO₂ phase is detected. The surface analyses of these samples by XPS show that, for most of them an unique chemical species (Sn⁴⁺) is found.      

Di-n-octyltin(IV) complexes with 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acid: Syntheses and assessment of solid state structures by Sn Mössbauer and X-ray diffraction and further insight into the solution structures using electrospray ionization MS, Sn NMR and variable temperature NMR spectroscopy

Reactions of 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acids (LHH′, where the aryl group is an R-substituted phenyl ring such that for L¹HH′: X = H; L²HH′: X=2′-OCH₃; L³HH′: X = 3′-CH₃; L⁴HH′: X = 4′-CH₃; L⁵HH′:X = 4′-Cl) with ⁿOct₂SnO in 2:1 and 1:1 molar ratios have been investigated. Two types of complexes, ⁿOct₂Sn(LH)₂ and {[ⁿOct₂Sn(LH)]₂O}₂, were isolated and they have been characterized by ¹H, ¹³C, ¹¹⁹Sn NMR, ESI-MS, IR and ^119mSn Mössbauer spectroscopic techniques in combination with elemental analyses. The crystal structures of ⁿOct₂Sn(L¹H)₂ (1), {[ⁿOct₂Sn(L²H)]₂O}₂ (3) and {[ⁿOct₂Sn(L³H)]₂O}₂(4) were determined. The mononuclear complex 1 was found to adopt a skew-trapezoidal bipyramidal arrangement around the tin atom while 3 and 4 are centrosymmetric tetranuclear bis(dicarboxylatotetrabutyldistannoxane) complexes containing a planar Sn₄O₂ core in which two μ₃-oxo O-atoms connect an Sn₂O₂ ring to two exocyclic Sn-atoms. The solution structures were confirmed by ¹¹⁹Sn NMR spectroscopy by observing one tin resonance in compound 1 and two tin resonances in {[ⁿOct₂Sn(L⁵H)]₂O}₂ (5). {[ⁿOct₂Sn(L²H)]₂O}₂ (3) and {[ⁿOct₂Sn(L³H)]₂O}₂ (4) undergo very complex exchange processes in deuteriochloroform solution, which has been confirmed by variable temperature ¹H NMR spectroscopy. The cleavage of the most labile bond in the molecule was studied by ESI mass spectrometry.