Experimental Determination of the Isotherm at 15°C of the System Mg<Superscript>2+</Superscript>/Cl<Superscript>−</Superscript>, SO<Subscript>4</Subscript><Superscript>2</Superscript>–H<Subscript>2</Subscript>O

Summary.  The diagram of the ternary system Mg²⁺/Cl⁻, SO₄ ²⁻–H₂O was established at 15°C by means of analytical and conductimetric measurements. Three compounds were found in this diagram, which are MgSO₄·6H₂O, MgSO₄·7H₂O, and MgCl₂·6H₂O. The solubility field of MgSO₄·7H₂O is important whereas those of MgSO₄·6H₂O and MgCl₂·6H₂O are small. The compositions (mass-%) of the two invariant points determined by the two methods are: MgSO₄:MgCl₂=2.73:33.80 and MgSO₄: MgCl₂=3.38:28.91. Both the measured and the calculated isotherm at 15°C have been used for modelling of the diagram Mg²⁺/Cl⁻, SO₄ ²⁻–H₂O between 0 and 35°C. The polythermal invariant point was approximately located between 15 and 10°C.  Corresponding author. E-mail: ariguib@planet.tn Received October 16, 2002; accepted (revised) December 3, 2002 Published online April 24, 2003 RID="a" ID="a" Dedicated to Prof. Dr. Heinz Gamsj?ger on the occasion of his 70^th birthday     

Thermogravimetric analysis of wheatleyite Na<Subscript>2</Subscript>Cu<Superscript>2+</Superscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>·2H<Subscript>2</Subscript>O

Evidence for the existence of primitive life forms such as lichens and fungi can be based upon the formation of oxalates. These oxalates form as a film like deposit on rocks and other host matrices. The anhydrous oxalate mineral moolooite CuC₂O₄ as the natural copper(II) oxalate mineral is a classic example. Another example of a natural oxalate is the mineral wheatleyite Na₂Cu²⁺(C₂O₄)₂·2H₂O. High resolution thermogravimetry coupled to evolved gas mass spectrometry shows decomposition of wheatleyite at 255°C. Two higher temperature mass losses are observed at 324 and 349°C. Higher temperature mass losses are observed at 819, 833 and 857°C. These mass losses as confirmed by mass spectrometry are attributed to the decomposition of tennerite CuO. In comparison the thermal decomposition of moolooite takes place at 260°C. Evolved gas mass spectrometry for moolooite shows the gas lost at this temperature is carbon dioxide. No water evolution was observed, thus indicating the moolooite is the anhydrous copper(II) oxalate as compared to the synthetic compound which is the dihydrate.     

Interaction of [В<Subscript>10</Subscript>H<Subscript>10</Subscript>]<Superscript>2–</Superscript> and [В<Subscript>12</Subscript>H<Subscript>12</Subscript>]<Superscript>2–</Superscript> with nitro compounds

The interaction of the [B₁₀H₁₀]^2– and [B₁₂H₁₂]^2– anions with aliphatic and aromatic nitro compounds (RNO₂, where R = Et, n-Pr, i-Pr, tert-Bu, Ph) has been studied under irradiation with visible and UV light. It has been shown that, depending on the reaction conditions, both mono- and disubstituted nitro-closo-decaborates can be selectively obtained in yields up to 50%.     

Mercury complex [(HOCH<Subscript>2</Subscript>)<Subscript>3</Subscript>CNH<Subscript>3</Subscript>]<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> [HgI<Subscript>4</Subscript>]<Superscript>2−</Superscript>: Synthesis and structure

The complex [(HOCH₂)₃CNH₃] ₂ ⁺ [HgI₄]^2? (I) was synthesized by reacting (trioxymethyl)methylammonium iodide with mercury dioide (2: 1 mol/mol) in acetone. X-ray crystallography shows that the complex consists of two types of crystallographically independent [(HOCH₂)₃CNH₃]⁺ cations and tetrahedral anions [HgI₄]^2? (IHgI, 106.49(2)°–113.99(4)°; Hg-I, 2.7849(8)-2.8105(8) Å. [(HOCH₂)₃CNH₃]⁺ cations are linked via hydrogen bonds O…H-N and O-H…N (O…N, 2.84–2.92 Å) to form polymer chains, which are cross-linked with one another via anions (I…H, 2.81, 2.82 Å).     

Structural investigation of salts containing ions [Pd(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Superscript>2+</Superscript> and [IrF<Subscript>6</Subscript>]<Superscript>2–</Superscript>

Double complex salts (DCS) α-[Pd(NH₃)₄][IrF₆]·H₂O (P2₁/m, a = 6.3181(3) Å, b = 10.8718(5) Å, с = 7.4526(4) Å, β = 103.568(2)°), β-[Pd(NH₃)₄][IrF₆]·H₂O (P2₁/с, a = 8.5773(3) Å, b = 10.8791(4) Å, с = = 12.6741(3) Å, β = 122.497(2)°), [Pd(NH₃)₄]₃[IrF₆]₂Cl₂·H₂O (P-1, a = 7.6080(2) Å, b = 7.6274(2) Å, с = 11.8070(3) Å, β = 122.497(2)°), and [Pd(NH₃)₄]₂[IrF₆]NO₃ (Fm-3m, a = 11.21210(10) Å) have been synthesized and structurally characterized for the first time. The existence of polymorphs for the DCS has been revealed. The influence of the chemical composition of the initial reagents on the reaction course and, respectively, the products, has been demonstrated. A hypothesis on the influence of the second coordination sphere on the formation of one or the other polymorph of the DCS has been suggested. It has been shown that the series α-[Pd(NH₃)₄][МF₆]·H₂O (M = Pt, Pd) exhibits isostructurality.     

A theoretical study on the dynamics of the gas phase reaction of NH<Subscript>2</Subscript>(<Superscript>2</Superscript>B<Subscript>1</Subscript>) with HO<Subscript>2</Subscript>(<Superscript>2</Superscript>A″)

Quasi-classical trajectory calculations and stochastic one-dimensional chemical master equation simulation methods are used to study the dynamics of the reaction of amidogen radical [NH₂(²B₁)] with hydroperoxyl radical [HO₂(²A″)] on the lowest singlet electronic state. The title complex reaction takes place on a multi-well multichannel potential energy surface consisting of three deep potential wells and one van der Waals complex. In quasi-classical trajectory calculations a new analytical potential energy surface based on CCSD(T)/aug-cc-pVTZ//MPW1K/6-31+G(d,p) ab initio method was driven and used to study the dynamics of the title reaction. In quasi-classical trajectory calculations, the reactive cross sections and reaction probabilities are determined for 200–2000 K relative translational energies to calculate the rate constants. The same ab initio method was used to have the necessary data for solving the one-dimensional chemical master equation to calculate the rate constants of different channels. In solving the master equation, the Lennard-Jones potential model was used to form the collision between the collider gases. The fractional populations of different intermediates and products in the early stages of the reaction were examined to determine the role of the energized intermediates and the van der Waals complex on the dynamics of the title reaction. Although the calculated total rate constants from both methods are in good agreement with the reported experimental values in the literature, the quasi-classical trajectory simulation predicts the formation of NH₂O + OH as the major channel in the title reaction in accordance with the previous studies (Sumathi and Peyerimhoff, Chem. Phys. Lett., 263:742–748, 1996), while the stochastic master equation simulation predicts the formation of HNO + H₂O as the major products.     

Study on nonlinear kinetic and thermodynamics of oscillating reaction of amino Acid-BrO<Stack><Subscript>3</Subscript><Superscript>−</Superscript></Stack>-Mn<Superscript>2+</Superscript>-H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-acetone system

With the help of the kinetic parameters (the rate constant (k _in k _p) and the apparent activation energy (E _in E _p) of the oscillatory induction period and oscillation period) of the oscillating reaction using thirteen amino acids, leucine (Leu), threonine (Thr), arginine (Arg), lysine (Lys), histidine (His), alanine (Ala), glutamine (Glu), glycine (Gly), methionine (Met), cystine (Cys), tryptophan (Trp), serine (Ser) and tyrosine (Tyr), as organic substrates in amino acid-BrO₃⁻-Mn²⁺-H₂SO₄-acetone system, then based on the Oregonator model and the thermodynamics theory on irreversible process, the thermodynamic function (ΔH _in, ΔG _in, ΔS _in and ΔH _p, ΔG _p, ΔS _p) of these oscillating system are studied. The results indicate the entropy ΔS of these oscillating reaction are negative, thereby it is proved that the oscillating reaction is a noequilibrium system with dissipation structure in agreement with the character of the oscillating reaction from disorder to order in irreversible thermodynamics. These are satisfactorily to explain the experimental phenomena.     

Influence of ion size on the stability of chloroplumbates containing PbCl<Stack><Subscript>5</Subscript><Superscript>−</Superscript></Stack> or PbCl<Stack><Subscript>6</Subscript><Superscript>2−</Superscript></Stack>

The enthalpies of formation of PbCl₄, PbCl₅⁻ and PbCl₆²⁻, originating from quantum mechanics, have enabled the thermodynamic behaviour of these ions with respect to Cl-detachment to be assessed. The stability of salts containing PbCl₅⁻ and PbCl₆²⁻ as a function of the dimensions of these anions and complementary cations was studied using an approach combining the Kapustinskii-Yatsimirskii equation with basic thermochemical relationships. It was found that hexachloroplumbates of monovalent metal cations will not dissociate into metal chlorides and PbCl₄, provided the complementary cations are suitably large in size. Hexachloroplumbates of divalent metal cations have not yet been synthesised since no known metal cations attain the requisite large size. Such salts will not dissociate if the divalent metal cations are able to complex suitably large electron-donating ligands. The pentachloroplumbates of both monovalent and divalent metal cations are unstable, since no known metal cations have appropriately large ionic radii. The approach adopted appears to be useful for the examination of the thermal behaviour, stability and reactivity of chloroplumbates.     

Photochemistry of PtBr<Subscript>6</Subscript><Superscript>2−</Superscript> in aqueous solution

Photochemistry of the PtBr₆ ²⁻ complex in aqueous solution was studied by steady-state and laser flash photolysis (308 nm). The multistep photoaquation of the complex occurs in the nano-and microsecond time intervals without the formation of intermediate platinum(III) complexes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2277–2283, December, 2007.     

Isothermal solubility diagram of the 2Na<Superscript>+</Superscript>,Mg<Superscript>2+</Superscript>‖2Cl<Superscript>−</Superscript>, 2ClO<Stack><Subscript>3</Subscript><Superscript>‒</Superscript></Stack>-H<Subscript>2</Subscript>O quaternary system at 20 and 100°C

The solubility in the 2Na⁺,Mg²⁺‖2Cl⁻, 2ClO₃⁻-H₂O system was studied at 20 and 100°C and the solubility diagrams were plotted. New compounds were not found to form in the title quaternary reciprocal system. The sodium chloride field was observed to expand with rising temperature.     

Research on photosensitivity of benzoquinones and benzoquinoneimines in the sunlight/Fe<Superscript>2+</Superscript>/S<Subscript>2</Subscript>O<Subscript>8</Subscript><Superscript>2−</Superscript> system

This paper investigated the photodegradation characteristics of benzoquinones and benzoquinoneimines. The photosensitivity of benzoquinones and benzoquinoneimines were analyzed by measuring the yield of SO ₄ ^?· in a light/Fe²⁺/S₂O₈ ^2? system and the degradation mechanism of benzoquinones, then discussed benzoquinoneimines in light/Fe²⁺/S₂O₈ ^2? and light/S₂O₈ ^2? system. The results revealed that a more aggressive oxidation of benzoquinones and benzoquinoneimines by the sunlight/Fe²⁺/S₂O₈ ^2? method showed a more rapid and more complete removal of chromaticity than that of the UV/Fe²⁺/S₂O₈ ^2? method. It was showed that they were photosensitizers, and they could generate ¹O₂ and O ₂ ^?· which could promote the formation of SO ₄ ^?· and ^·OH in the sunlight system. Nevertheless, for benzoquinones, the sunlight/S₂O₈ ^2? method was superior to the UV/S₂O₈ ^2? method. For benzoquinoneimines, the sunlight/S₂O₈ ^2? method was inferior to the UV/S₂O₈ ^2? method. In addition, the yield of SO ₄ ^?· in the sunlight/Fe²⁺/S₂O₈ ^2? system was more than that of the UV/Fe²⁺/S₂O₈ ^2? system. Therefore, the photosensitivity of benzoquinones is superior to benzoquinoneimines in water treatment.     

Calorimetric study of the acidic character of V<Subscript>2</Subscript>O<Subscript>5</Subscript>–TiO<Subscript>2</Subscript>/SO<Subscript>4</Subscript><Superscript>2−</Superscript> catalysts used in methanol oxidation to dimethoxymethane

The surface acidic properties of sulfated vanadia–titania catalysts prepared by various methods were investigated by adsorption microcalorimetry, using ammonia as probe molecule. The acidic characteristics of the samples were shown to be strongly affected by the preparation method, calcination temperature, and sulfur content. The samples prepared by sol–gel and mechanical grinding exhibited higher acidity than co-precipitated samples. Moreover, increasing the calcination temperature of co-precipitated samples resulted in a decrease in surface area from 402 to 57 m² g⁻¹ and sulfur content from around 4 to 0.2 mass%, but up to a certain point generated a stronger acidity. The optimal calcination temperature appeared to be around 673 K.     

Invar<Superscript>®</Superscript> oxidation in CO<Subscript>2</Subscript>

In this article, corrosion of Invar^® in a static carbon dioxide atmosphere \( 2\times 1 0^{4} \le P_{{{\text{CO}}_{ 2} }} \le 10^{5} \,{\text{Pa}} \) has been studied between 1163 and 1263 K. At the beginning, after a short initial deceleration for weight gains Δm/S <0.5 mg cm^?2, oxidation kinetics were linear up to weight gains of about 4.0 mg cm^?2, and only wüstite Fe_1?x O was formed with a constant rate r (mg cm^?2 s^?1) \( r = \frac{{{\text{d}}\left( {\frac{\Updelta m}{S}} \right)}}{{{\text{d}}t}} = 0.41 \times P_{{{\text{CO}}_{ 2} }} \exp \left( {\frac{ - 198000}{RT}} \right) \) where R is the gas constant and t the time (s). Reaction mechanism is similar to that of the pure iron in analogous conditions, with the same rate limiting step i.e. external reaction of CO₂ with wüstite and outward diffusion of ions Fe²⁺ (not limiting). For weight gains Δm/S higher than 4 mg cm^?2, the limiting step changes, with an increase of the reaction rate and an internal oxidation. The origin of this mechanism change lies in the microcracks appearing in the oxide during its growth. Then, wüstite is no longer bound to the substrate; outward diffusion of ions Fe²⁺ stops and a topotactic transformation converts wüstite into magnetite.     

Single-phased white-light emitting CaAl<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>8</Subscript>: Eu<Superscript>2+</Superscript>, Mn<Superscript>2+</Superscript> phosphors prepared by a sol–gel method

CaAl₂Si₂O₈: Eu²⁺, Mn²⁺ phosphors have been prepared by a sol–gel method. X-ray diffractometer, spectrofluorometer and UV–Vis spectrometer were used to characterize structural and optical properties of the samples. The results indicate that anorthite (CaAl₂Si₂O₈) directly crystallizes at 1000 °C in the sol–gel process. CaAl₂Si₂O₈: Eu²⁺, Mn²⁺ phosphors show two emission bands excited by ultraviolet light. Blue (around 415 nm) and yellow (around 575 nm) emissions originate from Eu²⁺ and Mn²⁺, respectively. With appropriate tuning of Mn²⁺ content, CaAl₂Si₂O₈: Eu²⁺, Mn²⁺ phosphors exhibit different hues and relative color temperatures.     

Analysis of the aromaticity in extended systems formed from isoelectronic Al<Subscript>4</Subscript><Superscript>2−</Superscript> and C<Subscript>4</Subscript><Superscript>2+</Superscript> aromatic clusters

Inspired by carbo-benzene and its inorganic analogues, in the current work, the viability of extended systems (called carbomers) formed from aromatic small rings was studied. The aluminum aromatic cluster, Al₄^2?, and its isoelectronic carbon analogue, C₄²⁺, were employed as starting point. The insertion of alkynyl units into the Al–Al and C–C bonds results in the extended molecules named carbomers. These molecules were compared with the global minima structures, which were searched employing the genetic algorithm program, GEGA. The electronic delocalization (aromaticity) of the isomers was studied with the induced magnetic field (B^ind). The results showed that global minimum of C₁₂²⁺ (formed from C₄²⁺) was an unexpected diatropic structure which presented a similar magnetic response to the C₄²⁺ cluster. Also, optical properties of C₁₂²⁺ were computed.     

Structures of the complex ions [CuCl<Subscript>4</Subscript>]<Superscript>2−</Superscript> and [CuCl<Subscript>5</Subscript>]<Superscript>3−</Superscript>

The electronic structures of the complex ions [CuCl₄]^2? and [CuCl₅]^3? were analyzed in terms of the extended angular overlap model (AOM) with consideration to sd and pd mixing. The total antibonding orbital energies of these ions show no anomalies in the transition from a tetrahedron to a planar square [CuCl₄]^2? and from a trigonal bipyramid to a tetragonal pyramid [CuCl₅]^3?. Presumably, the existence of numerous intermediate forms of these complexes is mainly due to the packing effects rather than the electronic factors.     

Nucleophilic addition of aromatic amide oximes to [2-B<Subscript>10</Subscript>H<Subscript>9</Subscript>NCC<Subscript>2</Subscript>H<Subscript>5</Subscript>]<Superscript>–</Superscript> anion

A series of closo-decaborate anions containing an O-iminoacylamide oxime fragment were synthesized by nucleophilic addition of aromatic amide oximes to 2-propionitrilium closo-decaborate anion. The isolated compounds were characterized by IR, ¹H, ¹³C–{¹H}, and ¹¹B–{¹H} NMR, and mass spectra. The structure of (Ph₄P)[2-B₁₀H₉NH=C(Et)ON=C(NH₂)C₆H₄Me-2] was determined by single-crystal X-ray analysis.     

Computational studies of the interactions of I<Superscript>−</Superscript> and I<Subscript>3</Subscript><Superscript>−</Superscript> with TiO<Subscript>2</Subscript> clusters: implications for dye-sensitized solar cells

Abstract  

First principle density-functional theory calculations have been carried out on the interaction of I⁻ and I₃ ⁻ with TiO₂ anatase surfaces, modeled by finite clusters that range in size from 48 to 180 atoms. The total energy per TiO₂ unit and the HOMO-LUMO gaps decrease with increasing the size of the clusters. Both redox species (I⁻ and I₃ ⁻) are strongly adsorbed on the TiO₂ surface with the adsorbtion of I⁻ being stronger. Adsorption of triiodide leads to its dissociation. The positions of the HOMO and LUMO of the adsorbed systems shift negatively from their respective cluster values. Solvation effects have been modeled using the CPCM model. Introducing solvent reduces the shifting of HOMO and LUMO. Implications for dye-sensitized solar cells (DSSC) are discussed. Both the HOMO-LUMO shifting and the strong adsorption might affect the performance of the cell.     

Reaction of the [B<Subscript>10</Subscript>H<Subscript>9</Subscript>O<Subscript>2</Subscript>C<Subscript>4</Subscript>H<Subscript>8</Subscript>]<Superscript>–</Superscript> anion with C-nucleophiles

The reactions of 1,4-dioxane-substituted closo-decaborate anion ([B₁₀H₉O₂C₄H₈]^–) with metal acetylenides, diethyl malonate, ethyl acetoacetate, triethyl orthoformate, acetylacetone, and malonodinitrile were studied. The reactions were shown to be accompanied with substituent ring opening and attachment of the corresponding pendant functional group. The obtained compounds were characterized by various physicochemical methods (IR and polynuclear NMR spectroscopy, ESI mass spectrometry).