Phase equilibria in quasi-binary sections of the Tl-Sn-S system

Phase equilibria in quasi-binary sections of the Tl-Sn-S system: (I) Tl₄SnS₄-SnS, (II) Tl₂SnS₃-SnS, (III) S-Tl₄SnS₄, (IV) S-Tl₂SnS₃, (V) Tl-SnS, and (VI) Tl₂S-SnS were studied by differential thermal analysis and X-ray powder diffraction. It was found that systems I and II are characterized by the eutectic type of interaction, the phase diagrams of systems III and IV are of the eutectic type with a degenerate eutectic at the sulfur melting point, and the phase diagram of system V is of the fourth type according to Roozeboom. Phase equilibria in system VI were specified.     

Effet Mössbauer de 119Sn dans les systèmes SnSBaS et SnSTl2S

Tin-119 Mössbauer spectra have been recorded at liquid nitrogen and room temperatures for ternary sulfides isolated from the systems SnSBaS and SnSTl₂S. The chemical isomer shifts observed (2.8 – 3.4 mm/sec relative to BaSnO₃ at 293 K) are characteristic of divalent tin compounds. The data are consistent with the known structures of these compounds and are discussed with regard to the stereochemical activity of the tin(II) lone pair of electrons. For Tl₂Sn₂S₃ and Tl₄SnS₃ the Mössbauer parameters are interpreted in terms of direct population of conductance bands by nonbonding electron pairs.     

Tl2SnS3 — ein Thiostannat mit 1 ∞ -[SnS 3 2− ]-Ketten

Black, fibre-like crystals of Tl₂SnS₃ were obtained from the melt using high-purity elements. Tl₂SnS₃ is monoclinic, space group C 2/m witha=23.03 (1),b=3.834 (1),c=7.379 (3) Å, =94.07 (5)°;Z=4. The crystal structure was determined from single crystal diffractometer intensity data and refined to a conventionalR of 0.127 for 724 observed reflections. The crystal structure is of a new type. It is characterized by infinite chains, ₁ -[SnS ₃ ^2– ], formed by cornersharing SnS₄-tetrahedra. These chains run along [010], their translation period comprises one tetrahedron (Einerketten). The average Sn — S-distance is 2.397 Å. The Tl⁺-ions separating the thiostannate-chains have different sulfur coordination. The coordination figure of Tl(1) is a bicapped trigonal prism, Tl(2) is in the center of an irregular cube. A comparison of the thiostannate-chains with other simple chains built-up by corner-sharing tetrahedra is given.

Herrn Prof. Dr.Karl Schlögl zum 60. Geburtstag gewidmet.     

Etude de la tétracoordination de l'etain dans deux orthothiostannates: Na4SnS4 et Ba2SnS4 (α)

The crystal structure of Na₄SnS₄ and Ba₂SnS₄ (α) were determined.Na₄SnS₄ crystallizes in tetragonal system, space group $\text{P}\text{4}\text{2}{}_1\text{c}$ with parameters a = 7.837 Å, c = 6.950 Å, Z = 2 and Ba₂SnS₄ (α) in the monoclinic system, space group $\text{P2}{}_1\text{c}$ with a = 8.481 Å, b = 8.526 Å, c = 12.280 Å, β = 112.97° and Z = 4.In these compounds, the crystal structure is built up from discrete orthothiostannate tetrahedra SnS₄. The structure of Ba₂SnS₄ (α) is modified K₂SO₄β type.     

Elektronenüberführungs-, IR-, RAMAN- und Photoelektronenspektren sowie röntgenographische Untersuchungen von Tl2MO2S2 Tl2MOS3und TB2MS4 (MMo,W) sowie Photoelektronenspektren zahlreicher Übergangsmetallverbindungen zum Vergleich

The electron transfer, i. r., RAMAN and photoelectron spectra and the powder diagrams of Tl₂MO₂S₂, TI₂MOS₃ Tl₂MS₄ (M = Mo, W) and, in comparison, the photoelectron spectra of some other transition metal compounds The electron transfer, i. r., RAMAN and photoelectron spectra and the powder diagrams of Tl₂MoO₂S₂, Tl₂WO₂S₂, Tl₂MoOS₃, Tl₂WOS₃, Tl₂MoS₄ and Tl₂WS₄ are reported and discussed. The different methods allow a discussion of the strong polarising effect of the Tl(I) cation on the anions. For the purpose of comparison the photoelectron spectra of the salts Tl₃MX₄ (M = V, Nb, Ta; X = S, Se); Tl₂MO₄ (M = Mo, W); Cs₂MX₄, (M = Mo, W; X = S, Se) and other similar salts were also measured.     

Diagramme de phases du système Tl2OMoO3

Six thallium(I) molybdates with numerous allotropic modifications have been found in the binary system Tl₂OMoO₃; Tl₄MoO₅, Tl₂Mo₂O₇, Tl₈Mo₁₀O₃₄ (three forms), and Tl₂Mo₇O₂₂ (two forms) melt incongruently; Tl₂MoO₄ and Tl₂Mo₄O₁₃ which are trimorphic melt congruently. For the most part, the compounds were characterized by their powder diagram and by their IR spectrum which allowed comparisons with alkaline molybdates.     

Phase relations in the TlXTl2Se systems (X = Cl,Br, I) and the crystal structure of Tl5Se2I

Each of the quasibinary systems TlClTl₂Se, TlBrTl₂Se, and TlITl₂Se contains a region of solid solution up to 18 mole% Tl₂Se, which decomposes peritectically. The mixed crystals can be explained by a statistical substitution of Se by two I atoms on the fourfold sites of the Tl₂Se lattice. Compounds of the type Tl₅Se₂X were derived by complete substitution. Crystals of Tl₅Se₂I, suitable for a crystal structure determination, were grown by the Bridgman technique. Tl₅Se₂I is tetragonal, $\text{I4}\text{mcm}\text{; a = 866.3}\text{pm}\text{, c = 1346.3}\text{pm}\text{, Z = 4}$. The structure is an ordered variation of the In₅Bi₃ structure and isopuntal to the Cr₅B₃ type. The structure is formed basically by layers of Tl₂Se, in which strings of TlI are introduced. The compounds Tl₅Se₂Br (a = 861.1 pm, c = 1292.2 pm) and Tl₅Se₂Cl (a = 856.5 pm, c = 1273.3 pm) have probably very similar structures. A tendency for immiscibility in the TlXTl₂Se systems is shown by the existence of a miscibility gap in the system TlClTl₂Se and by the endothermic enthalpies of mixing in the system TlBrTl₂Se. In the TlITl₂Se system the compound Tl₆Se₄I system was encountered.     

Solid-phase equilibria and thermodynamic properties of the Tl2Se-As2Se3-Se system

The Tl₂Se-As₂Se₃-Se system in the equilibrium crystalline state was studied by differential thermal analysis, X-ray powder diffraction, and measurements of emf relative to a thallium electrode within the temperature range 300–400 K. An isothermal section of the phase diagram at 300 K was constructed. The formation of ternary compounds Tl₃AsSe₄, TlAsSe₂, and Tl₃AsSe₃ was confirmed, and the locations of their phase regions were determined. From the emf measurement data, the partial molar functions of thallium in alloys, the standard thermodynamic functions of formation, and the standard entropies of the above ternary compounds were calculated.     

Mixed‐Valence Thallium(I,III) Bromides The Crystal Structure of α—Tl2Br3

Thallium sesquibromide Tl₂Br₃ is dimorphic. Scarlet coloured crystals of α‐Tl₂Br₃ were obtained by reactions of aqueous solutions of TlBr₃ and Tl₂SO₄ in agarose gel. In case of rapid crystallisation of hydrous TlBr₃/TlBr solutions and from TlBr/TlBr₂ melts ß‐Tl₂Br₃ is formed as scarlet coloured, extremely thin lamellae. The crystal structures of both forms are very similar and can be described as mixed‐valence thallium(I)‐hexabromothallates(III) Tl₃[TlBr₆]. In the monoclinic unit cell of α‐Tl₃[TlBr₆] (a = 26.763(7) Å; b = 15.311(6) Å; c = 27.375(6) Å; β = 108.63(2)°, Z = 32, space gr. C2/c) the 32 Tl^III‐cations are found in strongly distorted octahedral TlBr₆ groups. The 96 Tl^I cations are surrounded either by four or six TlBr₆ groups with contacts to 8 or 9 Br neighbors. Crystals of β‐Tl₃[TlBr₆] by contrast show almost hexagonal metrics (a = 13.124(4) Å, b = 13.130(4) Å, c = 25.550(7) Å, γ = 119.91(9)°, Z = 12, P2₁/m). Refinements of the parameters revealed structural disorder of TlBr₆ units, possibly resulting from multiple twinning. Both structures are composed of Tl₂[TlBr₆]^— and Tl₄[TlBr₆]⁺ multilayers, which alternate parallel (001). The structural relationships of the complicated structures of α‐ and β‐Tl₃[TlBr₆] to the three polymorphous forms of Tl₂Cl₃ as well as to the structures of monoclinic hexachlorothallates M₃TlCl₆ (M = K, Rb) and the cubic elpasolites are discussed.     

Interaction in the systems TlBiSe<Subscript>2</Subscript>–Tl<Subscript>9</Subscript>BiSe<Subscript>6</Subscript>–PbSe and Tl<Subscript>9</Subscript>BiSe<Subscript>6</Subscript>–Tl<Subscript>4</Subscript>PbSe<Subscript>3</Subscript>–PbSe

Phase equilibria in the systems TlBiSe₂–Tl₉BiSe₆–PbSe and Tl₉BiSe₆–Tl₄PbSe₃–PbSe were studied by differential thermal, X-ray powder diffraction, and microstructural analyses. State diagrams of the quasi-binary sections Tl₉BiSe₆–Tl₄PbSe₃, TlBiSe₂–PbSe, and Tl₉BiSe₆–PbSe were constructed, and so were projections of liquidus surfaces and isothermal sections at 600 K for the secondary quasi-ternary systems TlBiSe₂–Tl₉BiSe₆–PbSe and Tl₄PbSe₃–Tl₉BiSe₆–PbSe. The coordinates of invariant points and the boundaries of solid solutions were determined.     

Z-scheme heterojunction of SnS2-decorated 3DOM-SrTiO3 for selectively photocatalytic CO2 reduction into CH4

The rapid recombination of photoinduced electron-hole pairs as well as the deficiency of high-energy carriers restricted the redox ability and products selectivity. Herein, the heterojunction of SnS₂-decorated three-dimensional ordered macropores (3DOM)-SrTiO₃ catalysts were in-situ constructed to provide transmit channel for high-energy electron transmission. The suitable band edges of SnS₂ and SrTiO₃ contribute to the Z-scheme transfer of photogenerated carrier. The 3DOM structure of SrTiO₃-based catalyst possesses the slow light effect for enhancing light adsorption efficiency, and the surface alkalis strontium is benefit to the boosting adsorption for CO₂. The in-situ introduced SnS₂ decorated on the macroporous wall surface of 3DOM-SrTiO₃ altered the primary product from CO to CH₄. The Z-scheme electron transfer from SnS₂ combining with the holes in SrTiO₃ occurred under full spectrum photoexcitation, which improved the excitation and utilization of photogenerated electrons for CO₂ multi-electrons reduction. As a result, (SnS₂)₃/3DOM-SrTiO₃ catalyst exhibits higher activity for photocatalytic CO₂ reduction to CH₄ compared with single SnS₂ or 3DOM-SrTiO₃, i.e., its yield and selectivity of CH₄ are 12.5 μmol g^-1 h^-1 and 74.9%, respectively. The present work proposed the theoretical foundation of Z-scheme heterojunction construction for enhancing photocatalytic activity and selectivity for CO₂ conversion.     

Effect of co-anion on DC18C6-mediated Tl+ transport through an emulsion liquid membrane

Emulsion membrane systems consisting of an aqueous thallous salt source phase, a toluene membrane containing the macrocyclic ligand dicyclohexano-18-crown-6 (DC 18C6)(0.02M), the surfactant Span 80 (sorbitan monooleate) (3% v/v), and an aqueous 0.01M Li₄P₂O₇ receiving phase were studied with respect to the disappearance of Tl⁺ from the source phase as a function of time. The salts TlOH, Tl₂ CO₃, TlAu(CN)₂, TlSCN, TlClO₄, TlAg(CN)₂, Tl₄ Fe(CN)₆, TlF, Tl₂SO₄, TlBr, CH₂ (COOTl)₂, HCOOTl, TlCl, and TlNO₃ were investigated singly (salts listed in order of decreasing total percentage of Tl⁺ transport observed). In competitive transport experiments using equimolar TlAg(CN)₂ and TlAu(CN)₂, TlAu(CN)₂ was found to transport by a factor of six over TlAg(CN)₂. Attempts are made to explain the co-anion effect on Tl⁺ transport by relating transport inversely to the negative free energy of hydration of the co-anion, directly to the amount of ion pairing of the co-anion with a cationic species present, and directly to the amount of deprotonation of the surfactant.     

Darstellung,Eigenschaften, röntgenographische und spektroskopische Untersuchung von Tl4Nb2S11 und Tl4Ta2S11

On Polychalcogenides of Thallium with M₂Q₁₁ Groups as a Structural Building Block. I Preparation, Properties, X‐ray Diffractometry, and Spectroscopic Investigations of Tl₄Nb₂S₁₁ and Tl₄Ta₂S₁₁ The new ternary compounds Tl₄Nb₂S₁₁ and Tl₄Ta₂S₁₁ were prepared using Thallium polysulfide melts. Tl₄M₂S₁₁ crystallises isotypically to K₄Nb₂S_8.9Se_2.1 in the triclinic space group P 1 with a = 7.806(2) Å, b = 8.866(2) Å, c = 13.121(3) Å, α = 72.72(2)°, β = 88.80(3)°, and γ = 85.86(2)° for M = Nb and a = 7.837(1) Å, b = 8.902(1) Å, c = 13.176(1) Å, α = 72.69(1)°, β = 88.74(1)°, and γ = 85.67(1)° for M = Ta. The interatomic distances as well as angles within the [M₂S₁₁]^4– anions are similar to those of the previously reported data for analogous alkali metal polysulfides. Significant differences between Tl₄M₂S₁₁ and A₄M₂S₁₁ (A = K, Rb, Cs) are obvious for the shape of the polyhedra around the electropositive elements. The two title compounds melt congruently at 732 K (M = Nb) and 729 K (M = Ta). The optical band gaps were estimated as 1.26 eV for Tl₄Nb₂S₁₁ and as 1.80 eV for the Tantalum compound.     

Thallium(I)-Uranates(VI)

The solid state preparation, thermal and hydrolytic characteristics of thallium(I)—uranates(VI) are described. The phases identified were Tl₂UO₄, Tl₂U₂O₇ and a range of solid solution (Tl₂O. 2,33 UO₃? Tl₂O. 6 UO₃). The thallium uranates are isostructural with the corresponding potassium uranates. Tl₂U₂O₇ is the stable phase formed from the other uranates on hydrolytic treatment. The thallium uranates lose thallium(I) oxide on heating to temperatures above 750°C and the order of thermal stability is Tl₂U₆O₁₉～Tl₂U₃O₁₀～Tl₂U₂O₇»Tl₂UO₄.     

Reciprocal system 3Tl<Subscript>2</Subscript>S + Sb<Subscript>2</Subscript>Se<Subscript>3</Subscript> ⇆ 3Tl<Subscript>2</Subscript>Se + Sb<Subscript>2</Subscript>S<Subscript>3</Subscript>

Phase equilibria in the reciprocal system 3Tl₂S + Sb₂Se₃ ? 3Tl₂Se + Sb₂S₃ are investigated by DTA, X-ray powder diffraction, and emf measurements. Some polythermal sections, the isothermal section of the phase diagram at 400K, and the liquidus-surface projection for this system are constructed. The types and coordinates of invariant and univariant equilibria are determined. It is shown that the system is non-diagonal. Broad regions of solid solutions are found on the basis of the binary compounds Tl₂S and Tl₂Se and along the boundary system Sb₂S₃-Sb₂Se₃ and the sections Tl₃SbS₃-Tl₃SbSe₃, TlSbS₂-TlSbSe₂, and TlSb₃S₅-TlSb₃Se₅ of the phase diagram.     

Phase diagram of the Tl-TlI-S system and thermodynamic properties of the compound Tl<Subscript>6</Subscript>SI<Subscript>4</Subscript>

Phase equilibria in the Tl-TlI-S composition region of the Tl-S-I system were studied by differential thermal analysis, x-ray powder diffraction, and measurements of the microhardness and the emf of concentration circuits relative to a thallium electrode. A series of polythermal sections, an isothermal section at 300 K, and a projection of the liquidus surface were constructed. Primary crystallization regions of six phases, including the ternary compounds Tl₆SI₄ and Tl₃SI, were outlined, and the types and coordinates of non- and monovariant equilibria were determined. It was shown that the ternary compound Tl₆SI₄ forms tie lines with Tl, TlI, Tl₂S, Tl₄S₃, and TlS in the subsolidus region and that the homogeneity region of Tl₆SI₄ below 400 K does not exceed 1 mol %. From the emf measurement data, the standard thermodynamic functions of formation and standard entropy of the compound Tl₆SI₄ were calculated: G _f,298⁰ = −601.7 ± 2.5 kJ/mol, ΔH _f,298⁰= −595.1 ± 4.0 kJ/mol, and S ₂₉₈⁰ = 672 ± 10 J/(mol K).     

Ternäre Thallium-Indium-Sulfide: Eine Zusammenfassung

Ternary Thallium Indium Sulfides: A Summary Combined thermal and X-Ray analyses in the ternary system Thallium—Indium—Sulfur show, that the two binary sections Tl₂S? In₂S₃ and TlS? InS contain ternary compounds with unique crystal structures. The chemical formulas of these ternary solids are TlIn₅S₈, TlIn₃S₅, TlInS₂ and Tl₃InS₃ for the section Tl₂S? In₂S₃ and TlIn₅S₆ as well as Tl₃In₅S₈ (metastable high temperature phase) for the section TlS? InS respectively. With TlIn₅S₇ an additional ternary solid could be detected, which is located outside the two sections. It is derived from the binary mixed valence compound In₆S₇ by complete substitution of In⁺ by Tl⁺. The following ionic formulations make the mixed valence character of the ternary Thallium—Indium-Sulfides reasonable: TlIn₅S₈ = Tl⁺(In³⁺)₅(S^2?)₈, TlIn₃S₅ = Tl⁺ (In³⁺)₃(S^2?)₅, TlInS₂ = Tl⁺In³⁺(S^2?)₂, Tl₃InS₃ = (Tl⁺)₃In³⁺ · (S^2?)₃, TlIn₅S₆ = Tl⁺([In₂]⁴⁺)₂In³⁺ (S^2?)₆, Tl₃In₅S₈ = 4 × [(Tl⁺)_0,75 · (In⁺)_0,25In³⁺(S^2?)₂], TlIn₅S₇ = Tl⁺[In₂]⁴⁺ (In³⁺)₃(S^2?)₇. All compounds contain Tl⁺-ions in a characteristic “lone pair coordination” of S^2? ions. Indium atoms however occur with the oxidation numbers +2 (formal, In₂ dumb bells with covalent In? In bonding) and +3 (with In³⁺ in tetrahedral and octahedral coordination of S^2?). Chemical preparation, crystal chemistry and general properties of the ternary solids are discussed, summarized and compared to each other.     

Les systèmes MFTlF3 (M = Li,Na, K)

A large number of new phases have been prepared and characterized in the MFTlF₃ system: Na₃TlF₆ isostructural with cryolite, Na₃Tl₂F₉, Na_xTl_1−xF_3−2x (0.425 ? x ? 0.565 at 500°C) and Na₅Tl₉F₃₂ related to the fluorite type, K₃TlF₆ with a structure similar to that of (NH₄)₃FeF₆, K₅Tl₃F₁₄ with the chiolite structure, Na_yTl_1−yF_3−2y (0.12 ? y ? 0.14 at 500°C) and K₂Tl₇F₂₃ affiliated to α-UO₃, KTlF₄, and KTl₂F₇.     

Reciprocal system 3Tl2S + Bi2Se3 ↔ 3Tl2Se + Bi2S3

The reciprocal system 3Tl₂S + Bi₂Se₃ ? 3Tl₂Se + Bi₂S₃ has been investigated by DTA, X-ray powder diffraction analysis, and emf measurements. Some polythermal sections and the isothermal section at 500 K of the phase diagram and the projection of the liquidus surface of this system have been constructed, and the types and coordinates of the invariant and univariant equilibria have been determined. The existence of wide regions of quaternary solid solutions based on the binary compounds Tl₂S, Tl₂Se, Bi₂S₃, and Bi₂Se₃, and solid solutions between the temary compounds TlBiS₂ and TlBiSe₂ have been established.     

Interactions and glass formation in the TlAs2Se4-Tl3As2Se3Te3 system

The TlAs₂Se₄-Tl₃As₂Se₃Te₃ system was studied using differential thermal analysis (DTA), powder X-ray diffraction, microstructure observation, and microhardness and density measurements. A phase diagram of the title system was constructed. This system is a quasi-binary join of the TlSe-As₂Se₃-As₂Te₃ quasi-ternary system. All alloys of the system under standard conditions are prepared in the glassy form. The system has a eutectic, which contains 50 mol % Tl₃As₂Se₃Te₃ and melts at 150°C. The TlAs₂Se₄-base solid solution in the system extends to 12 mol % Tl₃As₂Se₃Te₃, and Tl₃As₂Se₃Te₃-based solid solution extends to 20 mol % TlAs₂Se₄.