7553-56-2

Several oscillations are observed in the rotational state population of I2B 3Π(Ou+) produced in the photodissociation (I2)2 + hν -> I2(Bυ',J') + I2(X).The initial excitation is above the dissociation limit of th

Two 'hollow' B-site deficient perovskites, (TzH)11(H3PO2)Sn6I23 and (TzH)3Sn2I7 (TzH+ = 1,2,4-triazolium, H3PO2 = hypohosphorous acid), have been prepared. (TzH)11(H3PO2)Sn6I23 is the first example of a 2D layered structure of this type. Leaving the same reaction mixture for an extended time also affords the 3D derivative (TzH)3Sn2I7.

The formation of electronically excited molecular iodine from the two-photon photodissociation of CI4 and CHI3 was investigated using dispersed fluorescence and ab initio calculations. Molecular iodine was formed in the D, D', and E

A new class of layered alkali metal-MoO//3 bronzes, A//xMoO//3 (A equals Li, Na, K, Rb), with nearly the same unit cell parameters as the host oxide has been synthesized. This was accomplished by the solid state reaction of MoO//3 with alkali metal iodides around 575 K; Li//xMoO//3 absorbs H//2O causing an increase in the b parameter of the unit cell. Hexagonal potassium bronzes of W//1// minus //xMo//xO//3 are synthesized for the first time.

We have carried out a systematic study of the 248 nm excimer-laser photodissociation of small methyl iodide clusters in a free jet expansion.Ground electronic state I2 is formed from the photolysis of methyliodide dimers and detected via the laser induced fluorescence (LIF) excitation spectrum of the (B-X) transition.The internal energy of the I2 is approximately 2.5 kJ/mol and is the same for CH3I seeded in CO2, Ar, Xe, O2, and He, as well as for the neat expansion and deuterated sample.A room temperature flow cell experiment shows that the reaction channel I* + CH3I -> I2 + CH3I does not contribute to the measured I2 signal.The results strongly imply that a cluster-induced cooperative effect is responsible for the I2-producing chemistry.

Crystals of iodine-doped indium(III) and zirconium(IV) diphthalocyanines, [InPc2]I2 and [ZrPc2]I2, were grown directly in the reaction of In-Tl alloy or zirconium powder with 1,2-dicyanobenzene under a stream of iodine at about 200°C. Both partially oxidised diphthalocyaninato complexes crystallise in the P4/mcc space group of the tetragonal system with one molecule per unit cell. The space group of P4/mcc requires that the central metal ions are disordered in these structures. The crystal structures shown columnar pseudo-one-dimensional stacks of [InPc2] or [ZrPc2] units with a non-integral charge and linear chains of symmetrical triiodide I3- ions, which were detected by a Raman spectroscopy. The pseudo-one-dimensional aggregates of [InPc2]2/3+ or [ZrPc2]2/3+ as well as the chains of I3- ions are aligned along the [001] direction. The formal oxidation state of the Pc macrorings equals to ? -1.167 and ? -1.667 in indium(III) and zirconium(IV) diphthalocyaninato complexes. The EPR measurement shows a single sharp EPR line at g = 2.0028 and 2.0026 for the indium and zirconium complexes, respectively. The conductivity measurement on polycrystalline samples at room temperature equals 2.7-3.1 × 10-2 and 5.2-5.5 × 10-2 Ω-1 cm-1 for [InPc2]I2 and [ZrPc2]I2, respectively. The charge transport proceeds mainly along the pseudo-one-dimensional [MPc2]2/3+ aggregates. Both iodine-doped metallodiphthalocyaninato complexes exhibit non-metallic character in conductivity (dσ/dT > 0).

The vapor pressure in the KI-CoI2 system is determined by isobaric boiling point measurements. Calculated vapor pressure isotherms of the KI-CoI2 system show negative deviations from linearity. The vapor composition over pure CoIsub

A new method for the chemical generation of atomic iodine intended for use in a chemical oxygen-iodine laser (COIL) was investigated experimentally. The method is based on the fast reaction of hydrogen iodide with chemically produced chlorine atoms. Effects of the initial ratio of reactants and their mixing in a flow of nitrogen were investigated experimentally and interpreted by means of a computational model for the reaction system. The yield of iodine atoms in the nitrogen flow reached 70-100% under optimum experimental conditions. Gain was observed in preliminary experiments on the chemical generation of atomic iodine in a flow of singlet oxygen.

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The photolysis of n-C3F7I in the uv yields I (2P1/2) with a quantum yield of nearly 1 (ref. 1).The I(2P1/2) decay by spontaneous emission, in collisions with the n-C3F7I by spin-orbit relaxation, and by a three body reaction with the newly formed I(2P3/2), yielding I2(B3?ou+).For the latter process the rate constant was determined to be k3=(10+/-5)*1E-33cm6 molec.-2s-1 Further an upper limit of the rate constant for a possibile bimolecular reaction of I(2P1/2) with n-C3F7I yielding I2 (X1Σog+) is given k53 molec.-1s-1

Peroxynitrous acid was reduced by cathodic linear sweep voltammetry at a gold electrode and by iodide at pH 3.2 and 5.6. The cathodic reduction wave was identified by measuring its decay in time, which was the same as observed by optical spectroscopy. The iodide oxidation was followed by optical measurement of the triiodide formation. Both reductions show one-electron stoichiometry, with the product nαα = 0.23 ± 0.04 from the electrochemical experiments, in which α is the transfer coefficient and na the number of electrons transferred, and an diiodine yield of ca. 0.5 equiv per equivalent of peroxynitrous acid. The voltammetric reduction was irreversible up to scan rates of 80 V s-1. Both reductions were pH independent in the range studied. The voltammetric reduction is most likely an irreversible elemental reaction followed by a chemical decay that cannot be observed directly. Because of the pH independence, we conclude that both reductions have a common short-lived intermediate, namely [HOONO]-. We estimate the electrode potential of the likely ONOOH/ONOOH- couple to be larger than 1 V. The commonly used electrode potential E°(ONOOH, H +/NO2, H2O) does not describe the chemistry of peroxynitrous acid.

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A Cr8 metallacrown binds halogens X2 (Cl2, Br2 and I2) without loss of crystallinity; the binding has been studied by X-ray diffraction and thermodynamic techniques.

The system H2O2, IO3-, H+, Mn2+ is a subsystem (no malonic acid) of the Briggs-Rauscher oscillator.As H2O2 disproportionates, iodine is initially produced and then after a long time is reoxidized to iodate.The initial rate of iodate reduction is highly dependent on and 2+>.Whwn crotonic acid is present in the subsystem to prevent I2 from forming, the rate of iodate reduction is highly dependent on -> and 2+>, and disproportionation of H2O2 is greatly reduced.With addition of iodine-oxidation steps, the skeleton model of Noyes and Furrow, and of DeKepper and Epstein, which predicts oscillations in the full Briggs-Rauscher system, reproduces behavior of the subsystem with and without crotonic acid.The scheme also reproduces oxidation of I2 by H2O2 in the H2O2, IO3-, H+, I2 system, though O2 evolution in the model is too high.

Selective iodocyclization of 6-(alkenylamino)-1-allylpyrazolo[3,4-d]pyrimidines provided hydrogenated derivatives of 1-allyl-8(9)-iodomethylimidazo(pyrimido)[1,2-a]pyrazolo[4,3-e]pyrimidines which were further reacted with NaN3 at 75°С to 80°С to give a series of new-type 1,3,6-triazocines annulated with the pyrazole, pyrimidine, imidazole (or pyrimidine), and 1,2,3-triazole rings. The compounds synthesized were structurally characterized by analytical, spectral (IR, 1H and 13C NMR, HPLC-mass), and X-ray diffraction data.

Behavior of CsI radioaerosols produced by CsI sublimation from a platinum support in argon, air, and water vapor-air mixture was studied. During 10-12 min of the vaporization at 900-1570 K, CsI radioaerosols undergo oxidative hydrolysis with atmospheric oxygen and water vapor to form CsOH aerosols and I2. The cesium-to-iodine ratio determined in various fractions shows that oxidation of CsI in argon is minimal and is caused by the presence of oxygen and water traces. Oxidative hydrolysis of CsI strongly increases with increasing water vapor content in the vapor-gas flow. The degree of oxidative hydrolysis of CsI in the gas flow depends not only on the content of water vapor and oxygen but also on the initial CsI/O2 molar ratio.

The determination of ozone decomposition rate by flow injection analysis (FIA) was investigated.Under the conditions studied a sampling rate was about 43 samples/h and the pseudo-first-order kinetic plot of the obtained data showed a good linearity.This FIA method seems to be useful for kinetic measurement of ozone decomposition in water.

Five new d0 transition metal iodates, BaTi(IO3) 6, LaTiO(IO3)5, Ba2VO 2(IO3)4·(IO3), K 2MoO2(IO3)4, and BaMoO 2(IO3)4· H2O, have been synthesized by hydrothermal methods using Ba(OH)2·8H 2O, La2O3, K2CO3, TiO2, V2O5, MoO3, and HIO 3 as reagents. The structures of these compounds were determined by single-crystal X-ray diffraction. All of the reported materials have zero-dimensional or pseudo-one-dimensional crystal structures composed of MO6 (M = Ti4+ , V5+, or Mo6+) octahedra connected to IO3 polyhedra. Infrared and Raman spectroscopy, thermogravimetric analysis, and UV-vis diffuse reflectance spectroscopy are also presented. Crystal data: BaTi(IO3)6, trigonal, space group R-3 (No. 148), with a = b = 11.4711(10) A, c = 11.1465(17) A, V = 1270.2(2) A3, and Z = 3; LaTiO(IO 3)5, monoclinic, space group P21/n (No. 14), with a = 7.4798(10) A, b = 18.065(2) A, c = 10.4843(14) A, β = 91.742(2)°, V = 1416.0(3) A3, and Z = 4; Ba 2VO2(IO3)4·(IO3), monoclinic, space group P21/c (No. 14), with a = 7.5012(9) A, b = 33.032(4) A, c = 7.2150(9) A, β = 116.612(2)°, V = 1598.3(3) A3, and Z = 4; K2MoO2(IO 3)4, monoclinic, space group C2/c (No. 15), with a = 12.959(2) A, b = 6.0793(9) A, c = 17.748(3) A, β = 102.410(4)°, V = 1365.5(4) A3, and Z = 4; BaMoO 2(IO3)4·H2O, monoclinic, space group P21/n (No. 14), with a = 13.3368(17) A, b = 5.6846(7) A, c = 18.405(2) A, β = 103.636(2)°, V = 1356.0(3) A3, and Z = 4.

In u.v. irradiated aqueous suspension of anatase, I- ion are oxidised in the presence of O2 at a conversion ca. 80 times greater than that for Br- ions, whereas Cl- ions withstand oxidation.The quantum yields (ca. 2percent for I-) have been determined and discussed.The nature of the final products depends on the pH, i.e., halogens or hypohalite ions in acidic or basic medium, respectively.However, the kinetics of the oxidation is not greatly influenced by the pH varying from 0 to 14.The reaction rate is proportional to the surface coverage in halide ions which is of the Langmuir type.We tentatively suggest that the reaction proceeds via the neutralization of absorved O- ions by photogenerated holes producing activated oxygen species which oxidize adsorbed halide ions into hypohalite ions.

The new tungstatoiodate, α-[H5W18O 59(IO3)]6-, containing IVO 3- within a {W18O54} metal oxide framework has been prepared and shown by X-ray crystallography and mass spectrometry to be derived from the fully oxidised [H3W 18O56(IO6)]6- by two-electron reduction accompanied by a redox-triggered structural rearrangement where three I-O covalent bonds are broken.

We present measurements of resistivity on Mo6 S3 I6 nanowire networks under different conditions. The room-temperature values of conductivity of as-grown nanowire networks are on the order of 300K =0.04 Sm and show linear current-voltage characteristics, indicating that-in agreement with band structure calculations-there is a finite density of states at the Fermi level. The conductivity of pristine samples is thermally activated, closely following three-dimensional variable range hopping (VRH) behavior of the form = 0 exp- (T0 T)Β, where Β=14. Removal of interstitial iodine from the network by annealing in a vacuum gives rise to a cross over to one-dimensional VRH with Β=12 and a concurrent increase in room-temperature conductivity. The introduction of water vapor leads to a decrease in conductivity and reveals that the resistivity of the network is sensitive to interstitial water molecules.

The oxidative addition of iodine to Pt(CN)42- is first-order with respect to iodide, iodine and complex. The reverse reductive elimination of iodide from trans-Pt(CN)4I22- is first-order with respect to iodide and Pt(CN)4I22-. The kinetics for the reaction between bromide and trans-Pt(CN)4ClH2O2- involves a rate-determining reductive elimination of chloride, followed by a rapid oxidative addition of bromine to the formed Pt(CN)42-. The reactions between trans-Pt(CN)4BrH2O- and bromide or chloride can be described as halide assisted anations. The rate constant for the bromide anation is kexp = k′[Br-]2 and for the chloride anation (in the presence of bromide) k′[Br-][Cl-] + k′' [Cl-]2. All reactions were followed using a stopped-flow technique at 25°C in 0.50M perchloric acid medium. The equilibrium constant for the redox equilibrium between Pt(CN)42-, iodine and Pt(CN)4I22- was determined separately to be (1.29 ± 0.03) × 104M-1. Exploratory stopped-flow experiments indicate that the oxidative addition of chlorine to PtCl22- is first-order with respect to both chlorine and tetrachloroplatinate. The experimental rate laws can be described by a reaction mechanism which resembles that introduced previously for Pt(II)-catalyzed anations and substitutions, in that both mechanisms can be considered as oxidative additions/reductive eliminations.

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The reaction of Me4EI (E = P, As), Me3EtSbI, Me2Et2SbI, MeEt3SbI, or Et4SbI with I2 in absence of solvent gives Me4PI3 (E = P, As), Me3EtSbI3, Me2Et2SbI3, MeEt3SbI3, or Et4SbI3, Me4SbI3 is formed in a reversible reaction by addition of I2 to (Me4Sb)3I8 or by reaction of a solution of Me4SbI in ethanol with I2 in benzene. The crystal structures of Me4HI3 (E = P, Sb), and Me3EtSbI3 and the syntheses of the novel compounds are reported.

The irradiation with ultraviolet light of CdI//2 containing 1-5 mole% CuI induces new absorption bands in the visible part of the spectrum. The absorption spectra of uncolored, optically colored, and thermally bleached CdI//2:CuI are presented and discussed. The optical coloration is due to the photoneutralization of Cu** plus ions in CdI//2, and the thermal bleaching is due to thermal ionization of Cu atoms. During the coloration process small microcrystals of metallic Cu are formed in the CdI//2 single crystals. Uncolored CdI//2:CuI shows luminescence similar to CdI//2. Optically colored CdI//2:CuI does not show luminescence, due to the presence of optically induced luminescence killing centers.

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A new dinuclear Cu(II) complex (1) was synthesized and crystallographically characterized. Each of the Cu(II) centres has penta coordination and been found to adopt square pyramidal geometry. Variable temperature magnetic measurements showed that there is weak ferromagnetic interaction between the Cu(II) centres in 1. 1 shows catecholase as well as phenoxazinone synthase activities in different solvents. The turn over numbers for the catecholase activity were 4.02 × 103 h?1 (MeOH) and 9.57 × 103 h?1 (MeCN), and that of phenoxazinone synthase activity were 1.065 × 103 h?1 (MeOH), 2.13 × 102 h?1 (MeCN) and 2.844 × 103 h?1 (DCM).

Hybrid lead halide perovskites have emerged as promising active materials for photovoltaic cells. Although superb efficiencies have been achieved, it is widely recognized that long-term stability is a key challenge intimately determining the future development of perovskite-based photovoltaic technology. Herein, we present reversible and irreversible photodecomposition reactions of methylammonium lead iodide (MAPbI3). Simulated sunlight irradiation and temperature (40-80 °C) corresponding to solar cell working conditions lead to three degradation pathways: (1) CH3NH2 + HI (identified as the reversible path), (2) NH3 + CH3I (the irreversible or detrimental path), and (3) a reversible Pb(0) + I2(g) photodecomposition reaction. If only the reversible reactions (1) and (3) take place and reaction (2) can be avoided, encapsulated MAPbI3 can be regenerated during the off-illumination timeframe. Therefore, to further improve operational stability in hybrid perovskite solar cells, detailed understanding of how to mitigate photodegradation and thermal degradation processes is necessary. First, encapsulation of the device is necessary not only to avoid contact of the perovskite with ambient air, but also to prevent leakage of volatile products released from the perovskite. Second, careful selection of the organic cations in the compositional formula of the perovskite is necessary to avoid irreversible reactions. Third, selective contacts must be as chemically inert as possible toward the volatile released products. Finally, hybrid halide perovskite materials are speculated to undergo a dynamic formation and decomposition process; this can gradually decrease the crystalline grain size of the perovskite with time; therefore, efforts to deposit highly crystalline perovskites with large crystal sizes may fail to increase the long-term stability of photovoltaic devices.

Biohazards and chemical hazards as well as radioactive hazards have always been a threat to human health. The search for solutions to these problems is an ongoing worldwide effort. In order to control biohazards by chemical methods, a synthetically useful fused tricyclic iodine-rich compound, 2,6-diiodo-3,5-dinitro-4,9-dihydrodipyrazolo [1,5-a:5′,1′-d][1,3,5]triazine (5), with good detonation performance was synthesized, characterized, and its properties determined. This compound which acts as an agent defeat weapon has been shown to destroy certain microorganisms effectively by releasing iodine after undergoing decomposition or combustion. The small iodine residues remaining will not be deleterious to human life after 1 month.

A bromo-capped metal-metal bonded diruthenium(i,i) complex Ru2(CO)4(PIN)2Br2 (1) (PIN = 1-isopropyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazol-2-ylidene) generates bromine with N-bromosuccinimide (NBS) at room temperature. Cycloalkene and stilbene are readily brominated by stoichiometric reactions with 1 and NBS. An analysis of the dibrominated products suggests the formation of cyclic bromonium intermediates indicating in situ Br2 generation. Complex 2, an iodide analogue of 1, is also synthesized. The reaction of 2 with N-iodosuccinimide releases I2, which is confirmed by the starch-iodine test. The catalytic utility of 1 is examined for the bromination of phenol. Catalyst 1, in combination with NBS and base, exhibits regioselectivity towards monobrominated products. Furthermore, efficient olefin aziridination is demonstrated utilizing catalyst 1 in the presence of NBS, K2CO3 and TsNH2.

A series of dimeric thorium disulfides and diselenides have been prepared with sterically undemanding ancillary ligands. Five complexes, (py)6Th2I4(μ2-S2)2, (py)6Th2Br2(SC6F5)2(μ2-S2)2, (py)6Th2I4(μ2-Se2)2, (py)6Th2I2(SC6F5)2(μ2-Se2)2, and (py)6Th2Br2(SC6F5)2(μ2-Se2)2, were isolated in high yields by first reducing mixtures of I2, F5C6SSC6F5, PhSeSePh, or PhSSPh, and PhSeBr with elemental Th, followed by in situ ligand-based redox reactions with elemental sulfur or selenium. These are the first examples of thorium compounds with bridging dichalcogenide ligands. Attempts to prepare chloride derivatives gave mixtures of (py)4ThCl4 and either (py)6Th2Cl2(SC6F5)2(μ2-S2)2 or (py)8Th4Se4(SePh)4(SC6F5)4. All products were characterized by single-crystal and powder X-ray diffraction and IR, UV-visible, and NMR spectroscopy. A computational analysis of experimental 77Se NMR chemical shifts reveals that the solvated dimeric structures with two bridging dichalcogenides are maintained in solution. Thermolysis of (py)6Th2I4(μ2-Se2)2 leads to reduction of the bridging Se22- moieties, oxidation of the I- ligand, and formation of solid-state ThSe2 and I2.

It is reported that iodine volatilization can occur in any elemental analysis of total iodine by ICP-MS. This problem affects the accuracy of the results, and it has been neither rationalized nor solved up to now. In this work, the formation of volatile iodine compounds in concentrated acid solutions (nitric acid or aqua regia) under microwave heating was studied by UV–Vis spectrophotometry, linear sweep voltammetry, and cyclic voltammetry. It was evidenced that molecular iodine (I2) can unexpectedly form in concentrated hot HNO3solutions, irrespective of the starting iodine compound (iodide, iodate, periodate, 3-iodo-L-tyrosine, 3,5-diiodo-L-tyrosine dehydrate). I2is produced by the nitrogen oxides existing in these conditions. The formation of volatile iodine is minimized in aqua regia, as chloride is able to keep iodine in solution due to the formation of charged chloro-iodo complexes (e.g. I2Cl?). The dilution of the concentrated acid solution, required prior to the ICP-MS analysis, causes the disruption of I2Cl?so that I2can again volatilize. To avoid this, 0.1 M thiocyanate can be added, as it forms a strong I2SCN?complex which keeps I2in solution as ion. Also other iodine species possibly occurring in the explored conditions, iodide and iodate, were demonstrated to be converted to I2SCN?in diluted HNO3solutions and in the presence of 0.1 M thiocyanate. Recovery tests demonstrated that iodine volatilization is minimized if samples containing iodine are treated in aqua regia and, after dilution, they are added with 0.1 M thiocyanate.

Platinum supported on carbon as a catalyst is widely reported and have a wide range of applications ranging from fuel cell application to hydrogenation reactions, where structure and properties of carbon support play an important role in the functioning of the catalyst. Mesoporous carbon supported platinum nanocatalyst was synthesized by hard templating route using mesoporous silica as template. The catalyst prepared has been characterized by X-ray diffraction, Raman, SEM, TEM, XPS and BET surface area. This catalyst has been employed for liquid phase HI decomposition reaction of sulfur iodine thermochemical cycle for production of hydrogen. The catalyst was evaluated for its activity for HI decomposition reaction and stability in the reaction environment. From present study we conclude that Pt supported on mesoporous carbon is a suitable and stable catalyst for liquid phase HI decomposition reaction.

The complexes of pyridine-2-aldehyde-2-quinolylhydrazone Co(III) nitrate [Co(paqh)2](NO3)2, methyl-2-pyridylketone-2-quinolinhyrazone Co(III) nitrate [Co(mpkqh)2](NO3)2, and phenyl-2-pyridylketon-2-quinolinhyrazone Co(III) nitrate [Co(ppkqh)2](NO3)2 were prepared and characterized. Solubilities of Co(III)–hydrazone complexes were measured. Transfer chemical potentials were calculated from the measured solubilities of the Co(III) complexes in aqueous methanol mixtures at 25?°C. The reactivity trends in the transfer chemical potentials are discussed in terms of the nature of the bonded ligands. Kinetics of the base hydrolysis of Co(III)–hydrazone complexes in the aqueous methanol mixtures have been studied at 25?°C, and follow the rate law kobs?=?k2[OH?]. The solvent effects on the reactivity trends of Co(III) complexes are analyzed into initial state (is) and transition states (ts) components. The reaction rates are reduced by the increase of methanol content. The destabilization of the transition state is remarkable compared to the initial state in the aqueous methanol mixtures. The initial state is more hydrophobic in nature than the transition state for Co(III) complex reactions.

Energetic bridged triiodopyrazoles and triiodoimidazoles were designed and synthsized by reacting potassium triiodopyrazolate or triiodoimidazolate with corresponding dichloro compounds. All compounds were fully characterized by 1H and 13

Phosgene and its analogs are greatly harmful to the public health, environmental safety and homeland security as widely used industrial substances with extremely high toxicity. In order to rapidly evaluate the emergency risk caused by these chemicals, a new highly sensitive method based on surface-enhanced Raman spectroscopy (SERS) technique for measurement of phosgene agents was developed for the first time. Coupled with a chemical transformation approach, the highly toxic phosgene was conveniently converted to a SERS-sensitive probe, i.e. iodine (I2), with low toxicity or non-toxicity. The characteristic SERS peak in 459 cm-1 was used for quantitation and was presumed as a formation of triiodide anion (I3-), which was induced in an iodide (I-)-aggregation Au NPs system. The total measurement can be completed in ~20 min with the limits of detection of ~60 μg/l (phosgene) and ~30 μg/l (diphosgene), respectively, on a portable Raman spectrometer. This work is the first report of SERS measurement on phosgene and diphosgene in a quantitative level. This method is expected to meet the requirements of on-site detection of phosgene agents, promote emergency responses and raise more opportunities for the portable SERS applications. A sensitive surface-enhanced Raman spectroscopy method for measurement of phosgene agents with a chemical transformation approach was reported for the first time. With the transformed product iodine, a more stable triiodide anion was formed in an iodide-aggregated Au nanoparticles system appeared as a characteristic ultraviolet-visible absorption peak at 352 nm and a surface-enhanced Raman spectroscopy peak of 459 cm-1. Three phosgene agents exhibit different reaction rates.

Methods and apparatus for generation of dual biocides are provided. The electrolytic generation of chlorine as a biocide is employed for further generation of additional biocides within a single system or generator, including bromine, iodine, chlorine dioxide, fluorine, or chloramines from their respective salts and/or precursors. A single on-site generating system produces a combination of biocides for applications of use providing cost, safety and efficacy improvements. Methods of using the disinfecting biocides provide a synergistic effect through simultaneous or sequential applications.

The iodine-arsenous acid (Roebuck), iodide-iodate (Dushman), and iodate-arsenous acid reactions have been studied simultaneously by a stopped-flow technique by monitoring the absorbance-time profiles at the isosbestic point of the I2/I3- system (468 nm). Using the well-accepted rate coefficients of iodine hydrolysis, we have proven that iodine is the kinetically active species of the iodine-arsenous acid reaction. Strong iodide inhibition of this system is explained by a rapidly established equilibrium between iodine and arsenous acid to produce an iodide ion, a hydrogen ion, and a short-lived intermediate H2AsO3I, which is shifted far to the left. Taking into consideration the generally accepted kinetic model of the Dushman reaction where I2O2 plays a key role to account for all of the most important observations in this subsystem and a sequence of simple formal oxygen-transfer reactions between arsenous acid and iodic acid as well as iodous acid and hypoiodous acid, we propose a 13-step comprehensive kinetic model, including seven rapidly established equilibria with only six fitted parameters, that is able to explain all of the most important characteristics of the kinetic curves of all of the title systems both individually and simultaneously.

The aqueous photoreactions of three halide ions (chloride, bromide and iodide) were studied using a diode array spectrophotometer to drive and detect the process at the same time. The concentration and pH dependences of the halogen formation rates were studied in detail. The experimental data were interpreted by improving earlier models where the cage complex of a halogen atom and an electron has a central role. The triiodide ion was shown to exert a strong inhibiting effect on the reaction sequence leading to its own formation. An assumed chemical reaction between the triiodide ion and the cage complex interpreted the strong autoinhibition effect. It is shown that there is a real danger of unwanted interference from the photoreactions of halide ions when halide salts are used as supporting electrolytes in spectrophotometric experiments using a relatively high intensity UV light source.

A new family of fluorescent synthetic molecular probes for nitric oxide sensing based on ortho-hydroxyamino-triarylpyrylium salts is presented. This journal is the Partner Organisations 2014.

The reaction of Me3AsI2 with unactivated iron powder provides a synthetic entry into the coordination chemistry of iron(III) iodide, which is inaccessible by traditional routes due to the low stability of the parent halide FeI3. The reaction of iron powder with Me 3AsI2 results in the formation of a trigonal bipyramidal complex, [FeI3(AsMe3)2], which features the iodide ligands in the equatorial positions, and the Me3As groups occupying the axial positions. This complex is a rare example of an iron(III) iodide complex, and is the first iron(III) complex of a monodentate tertiary arsine ligand. The preparation of [FeI3(AsMe3) 2] via the direct oxidation of iron powder further demonstrates that complexes of soft donor ligands can be prepared with hard transition metal centres, such as iron(III), in direct contravention of the HSAB principle. The structure of [FeI3(AsMe 3)2] is isomorphous with all previously reported [MX 3(EMe3)2] (M = main group or transition metal, X = halide, E = N, P, As) trigonal bipyramidal structures.

Humic substances that preferentially adsorb at the air/water interfaces of water or aerosols consist of both fulvic and humic acid. To investigate the chemical reactivity for the heterogeneous reaction of gaseous ozone, O 3(g), with aqueous iodide, I-(aq), in the presence of standard fulvic acid, humic acid, or alcohol, cavity ring-down spectroscopy was used to detect gaseous products, iodine, I2(g) and an iodine monoxide radical, IO(g). Fulvic acid enhanced the I2(g) production yield, but not the IO(g) yield. Humic acid, n-hexanol, n-heptanol, and n-octanol did not affect the yields of I2(g) or IO(g). We can infer that the carboxylic group contained in fulvic acid promotes the I2(g) emission by supplying the requisite interfacial protons more efficiently than water on its surface.

The incorporation of neptunium(VI) into the layered uranyl selenite Cs[(UO2)(HSeO3)(SeO3)] has yielded the highest level of neptunium uptake in a uranyl compound to date with an average of 12(±3)% substitution of NpVI for UVI. Furthermore, this is the first case in nearly 2 decades of dedicated incorporation studies in which the oxidation state of neptunium has been determined spectroscopically in a doped uranyl compound and also the first time in which neptunium incorporation has resulted in a structural transformation.

We report that rates of I2(g) emissions, measured via cavity ring-down spectroscopy, during the heterogeneous ozonation of interfacial iodide: I-(surface, s) + O3(g) + H+(s) →→ I2(g), are enhanced several-fold, whereas those of IO · (g) are unaffected, by the presence of undissociated alkanoic acids on water. The amphiphilic weak carboxylic acids appear to promote I2(g) emissions by supplying the requisite interfacial protons H+(s) more efficiently than water itself, at pH values representative of submicrometer marine aerosol particles. We infer that the organic acids coating aerosol particles ejected from oceans topmost films should enhance I2(g) production in marine boundary layers.

Thermal reaction between PhCCI and powdered Te afforded a mixture of (E)-4-iodo-2-(iodo(phenyl)-5-phenyl-1,3-ditellurofulvene (1) and (Z)-4-iodo-2-(iodo(phenyl)-5-phenyl-1-(diiodo),3-ditellurofulvene (2), which was subsequently reduced to (Z)-4-iodo-2-(iodo(phenyl)-5-phenyl-1,3- ditellurofulvene (3). Formation of 1 and 3 as the thermodynamically most stable products has been rationalized using density functional theory (DFT) calculations. Molecular structures of 1-3 were established crystallographically. In the solid state the coordination sphere of both tellurium atoms in 2 is extended by weak intermolecular Te?π interactions with the solvate molecule of toluene which completes the pseudo-trigonal bipyramidal coordination geometry around each Te atom and assembles 2 into the chains along the crystallographic c-axis.

A new potential infrared (IR) nonlinear optical (NLO) material Bi 2(IO4)(IO3)3 was synthesized by hydrothermal method. Bi2(IO4)(IO3)3 crystallizes in the chiral orthorhombic space group P212 121 (No. 19) with a = 5.6831(11) A, b = 12.394(3) A, and c = 16.849(3) A. It exhibits a threedimensional framework through a combination of the IO3, IO4, BiO8, and BiO9 polyhedra and is the first noncentrosymmetric (NCS) structure containing [IO4]3- anion. Bi2(IO 4)(IO3)3 has an IR cutoff wavelength of 12.3 ?m and belongs to the type 1 phase-matchable class with a moderately large SHG response of 5 × KDP, which is in good agreement with the theoretical calculations.

A method comprising: providing a first halogen stream; providing a first alkane stream; reacting at least a portion of the first halogen stream with at least a portion of the first alkane stream in a first reaction vessel to form a first halogenated stream; providing a second alkane stream comprising C2 and higher hydrocarbons; providing a second halogen stream; and reacting at least a portion of the second halogen stream with at least a portion of the second alkane stream in a second reaction vessel to form a second halogenated stream.

A new metabolite of the biologically active thiocarbamide dimethylthiourea (DMTU) has been synthesized and characterized. DMTU's metabolic activation in the physiological environment is expected to be dominated by S-oxygenation, which produces, successively, the sulfenic, sulfinic, and sulfonic acids before forming sulfate and dimethylurea. Only the sulfinic and sulfonic acids are stable enough to be isolated. This manuscript reports on the first synthesis, isolation, and characterization of the sulfonic acid: dimethylaminoiminomethanesulfonic acid (DMAIMSOA). It crystallizes in the orthorhombic Pbca space group and exists as a zwitterion in its solid crystal form. The negative charge is delocalized over the sulfonic acid oxygens and the positive charge is concentrated over the planar N-C-N framework rather than strictly on the sp2-hybridized cationic carbon center. As opposed to its sulfinic acid analogue, DMAIMSOA is extremely inert in acidic environments and can maintain its titer for weeks at pH 6 and below. It is, however, reasonably reactive at physiological pH conditions and can be oxidized to dimethylurea and sulfate by mild oxidants such as aqueous iodine.

Bis(NHC)-Pd(II) complexes derived from l,l'-binaphthyl-2,2'-diamine (BINAM) were successfully first used to catalyze the dioxygenation of alkenes under mild conditions tolerant of air and moisture. Cationic NHC-Pd2+ diaquo complex 1e showed the highest catalytic activity to give 1,2dioxygenation products with good syn-diastereoselectivity for 1,2-disubstituted alkenes.

The fast reaction of gaseous ozone, O3(g), with aqueous iodide, I-(aq), was found to be affected by environmentally relevant cosolutes in experiments using cavity ring-down spectroscopy (CRDS) and electrospray ionization mass spectrometry (ESIMS) for the detection of gaseous and interfacial products, respectively. Iodine, I2(g), and iodine monoxide radical, IO(g), product yields were suppressed in the presence of a few millimolar phenol (pKa = 10.0), p-methoxyphenol (10.2), or p-cresol (10.3) at pH 3 but unaffected by salicylic acid (pKa2 = 13.6), tert-butanol, n-butanol, or malonic acid. We infer that reactive anionic phenolates inhibit I2(g) and IO(g) emissions by competing with I -(aq) for O3(g) at the air/water interface. ESIMS product analysis supports this mechanism. Atmospheric implications are discussed.

The kinetic study of the oxidation of iodide ion by V(V) has been carried out in the water pools of cetyl trimethyl ammonium bromide(CTAB) reverse micelles in a mixture of chloroform-hexane (3 : 2). The study of the effect of concentration of V(V) and I- on rate show that the reaction obeys first order kinetics with each of the reactants. A plot of k′ (pseudo first order rate constant) versus [H+] is linear with a positive intercept at constant concentrations of iodide and bromide. The rate of the reaction is markedly increased in the reverse micellar medium compared to conventional aqueous medium under identical conditions. The pronounced acceleration in reverse micelles has been accounted for by the concentration effect in the water pool which have an effect on kinetics.

Thermal decomposition of the energetic ionic liquids 1-methyl-4-amino-1,2, 4-triazolium iodide (Me4ATI), 1-methyl-4-amino-1,2,4-triazolium nitrate (Me4ATN), 1-amino-3-methyl-1,2,3-triazolium iodide (Me1ATI), and 1-amino-3-methyl-1,2,3-triazolium nitrate (Me1ATN) was studied by confined rapid thermolysis. Sub-milligram quantities of the compounds were subjected to decomposition under isothermal conditions achieved by initially heating the sample at rates of approximately 2000 K/s. The products formed by decomposition under the afore-mentioned conditions were sampled by rapid scan FTIR spectroscopy and time-of-flight mass spectrometry. Decomposition studies involving the iodide salts were carried out around 270-290.C, whereas the nitrate salts were subjected to 320-340.C. The amino group was found to be involved in the initiation reaction, forming copious quantities of ammonia from the iodide compounds and, N2O and H2 O from the nitrate compounds. The extent of decomposition of the triazole ring was minimal at the considered temperatures.

Structurally diverse alcohols and phenols were trimethylsilylated in a clean and efficient reaction with hexamethyldisilazane (HMDS) based on the use of I2 generated in situ from Fe(NO3)3 · 9 H2O/NaI. The reaction occurs very rapid in good-to-high yield in CH2Cl2 at room temperature, and the use of toxic and corrosive molecular I2 is avoided.

The oxidation of methionine (Met) by acidic iodate and aqueous iodine was studied. Though the reaction is a simple two-electron oxidation to give methionine sulfoxide (Met-S=O), the dynamics of the reaction are, however, very complex, characterized by clock reaction characteristics and transient formation of iodine. In excess methionine conditions, the stoichiometry of the reaction was deduced to be IO3- + 3Met → I- + 3Met-S=O. In excess iodate, the iodide product reacts with iodate to give a final product of molecular iodine and a 2:5 stoichiometry: 2IO3 - + 5Met + 2H+ → I2 + 5Met-S=O + H 2O. The direct reaction of iodine and methionine is slow and mildly autoinhibitory, which explains the transient formation of iodine, even in conditions of excess methionine in which iodine is not a final product. The whole reaction scheme could be simulated by a simple network of 11 reactions.

Recent studies indicated that gaseous halogens mediate key tropospheric chemical processes. The inclusion of halogen-ozone chemistry in atmospheric box models actually closes the ～50% gap between estimated and measured ozone losses in the marine boundary

The enhancement of sonochemical-reaction efficiency by pulsed ultrasound at 152 kHz has been studied experimentally through absorbance measurements of triiodide ions from sonochemical oxidation of potassium iodide at different liquid volumes to determine

A process reduces the microbial content in land mass by providing molecular iodine in the land mass in a concentration in aqueous material in the land mass of at least 5 or 10 parts per million. The molecular iodine may be added in gaseous or liquid or solid state, and may be formed in situ using available water, added water and/or alcohol in the reaction.

With natural sunlight TiO2 (anatase), ZrO2, MoO3, Fe2O3, ZnO, CeO2 and Al2O3 microparticles photocatalyze the oxidation of iodide ion but CuO, ZnS, CdO, CdS, HgO, PbO,

Disclosed is a means for preventing the release of I2 during the production or storage of a 1,3-diiodohydantoin compound to thereby prevent the reduction in purity of the compound or overcome various disadvantages caused by I2. A process for producing a 1,3-diiodohydantoin compound comprising the steps of providing a wet material containing the 1,3-diiodohydantoin compound, and (1) contacting the wet material with a heated air to dry the wet material or (2) lyophilizing the wet material; a method for storage of a 1,3-diiodohydantoin compound comprising the step of storing the 1,3-diiodohydantoin compound under the temperature condition of 15?C or lower; and a 1,3-diiodohydantoin compound having a free I2 content of 1% by mass of less.

Ion-detecting sensors for detecting a target ion in a sample are provided. The sensor comprises a plasticizer-free copolymer comprised of polymerized units of methacrylate monomers having pendent alkyl groups of different length and a functionalized ionophore of said ion, wherein at least a portion of the functionalized ionophore is grafted into the copolymer through covalent linkages. Sensors may comprise ionophores such as hydrophilic crown ethers or functionalized derivative of 3-oxapentandiaminde-type ionophores. This invention further provides sensors for detecting target ions in a sample, comprising plasticizer-free molecularly imprinted polymers, wherein the polymers comprise polymerized units of methacrylate monomers having pendent alkyl groups of different length and a functionalized ionophore of said ion. In particular, a magnesium ion sensor comprising a functionalized derivative of a 3-oxapentandiaminde-type calcium ion-selective ionophore is provided. Sensors of this invention include carrier-based ion-selective electrodes or optodes such as thin film ion-specific optodes, particle-based optodes, or bulk optodes.

A method of the chemical generation of atomic iodine for a chemical oxygen-iodine laser (COIL) using atomic fluorine as a reaction intermediate was studied experimentally. This method is based on the reaction between F2 and NO providing F atoms, and the reaction of F with HI resulting in iodine atoms generation. Atomic iodine was produced with efficiency exceeding 40% relative to initial F2 flow rate. This efficiency was nearly independent on pressure and total gas flow rate. The F atoms were stable in the reactor up to 2 ms. An optimum ratio of the reactants flow rates was F2:NO:HI = 1:1:1. A rate constant of the reaction of F2 with HI was determined. The numerical modelling showed that remaining HI and IF were probably consumed in their mutual reaction. The reaction system was found suitable for employing in a generator of atomic iodine with its subsequent injection into a supersonic nozzle of a COIL.

The kinetics of the periodate-iodide reaction has a contradictory history dating back to almost a century. This reaction has been reinvestigated spectrophotometrically in the pH range 3.13-5.55 in both buffered (acetic acid/acetate) and unbuffered solution at T = 25.0 ± 0.1 °C with an I = 0.5 M ionic strength. The spectra between 290 and 500 nm were recorded and the reaction was followed until at least 95% of one of the reactants was consumed. The stoichiometry has been found to be strongly dependent on pH, but the rate of the initial step is independent of pH within the pH range studied. An eight-step kinetic model is proposed with four fitted kinetic parameters to take all the important characteristics of the experimental curves into account. On the basis of the model, a perfect reconciliation of the previous contradictory results is presented. It is shown that the kinetic parameters obtained from the initial rate of formation of a product unavoidably leads to misinterpretation of the results in the case of a branching mechanism (and stoichiometry).

The effect of freezing on a variety of acidified and neutral, nitrite ion and halide-containing mixtures has been investigated using UV/vis spectroscopy. Several trihalide ions were formed and monitored, including I2Cl -, I2Br-, ICI2- and IBr2-. A mechanism to explain the observations is given in terms of steps involving INO and the nitroacidium ion, [H2ONO] +. The transformation of sea salt components to specific trihalide ions by freezing represents a potentially important process in a polar atmospheric context. This is because the dichloro- and dibromo-trihalide ions can release chlorine- and bromine-containing gases, which are key intermediates in ozone destruction.

Reaction probabilities of gaseous nitrous acid, HONO, with HCl, HBr, and HI treated ice surfaces have been investigated in a fast flow-tube reactor coupled with a differentially pumped quadrupole mass spectrometer (QMS) at 191 K. The reaction probability increases with the HX surface coverage, and the rate is the highest for the HONO reaction on the Hi-treated ice surface. Relative rate constants are correlated to the nucleophilic parameter, according to the linear free-energy relationship for this series of heterogeneous reactions on ice surfaces. The correlation was also extended to HOCl + HX(ad) reactions on the ice surface, and it can be used to treat other heterogeneous atmospheric and catalytic reactions. The reaction products ClNO and BrNO were determined by the QMS. INO was found to rapidly convert to I2 on surfaces, and I2 was observed from the reaction of HONO + HI. The uptake coefficient of I2 on the HI-treated ice surface is higher than that for I2 on the water-ice surface.

The present invention relates to a method for processing of hydrogen for the reductive acylation of nitro, azido and cyano arenes. More particularly, this invention relates to an improved process for the preparation of amides and anilides using C3-C7 carboxylic acids as proton source/acylating agents employing Fe3+-montmorillonite as a catalyst.

A method for processing of hydrogen for the reductive acylation of nitro, azido and cyano arenes is disclosed. More particularly, improved process for the preparation of amides and anilides using C3-C7carboxylic acids as proton source/acylating agents employing Fe3+-montmorillonite as a catalyst is disclosed.

We report the observation of the spontaneous formation of a cellular structure in a simple inorganic system. The system is obtained by immersing a pellet of calcium and copper chlorides in an alkali solution containing sodium carbonate, sodium iodide, and hydrogen peroxide. The system produces a cell surrounded by a semipermeable membrane. Reactants diffuse and react inside the cell with copper ions serving as catalyst. The products diffuse out of the cell. The system sustains itself far from thermodynamic equilibrium.