Mechanism of perchlorate formation on boron-doped diamond film anodes.

This research investigated the mechanism of perchlorate (ClO(4)(-)) formation from chlorate (ClO(3)(-)) on boron-doped diamond (BDD) film anodes by use of a rotating disk electrode reactor. Rates of ClO(4)(-) formation were determined as functions of the electrode potential (2.29-2.70 V/standard hydrogen electrode, SHE) and temperature (10-40 °C). At all applied potentials and a ClO(3)(-) concentration of 1 mM, ClO(4)(-) production rates were zeroth-order with respect to ClO(4)(-) concentration. Experimental and density functional theory (DFT) results indicate that ClO(3)(-) oxidation proceeds via a combination of direct electron transfer and hydroxyl radical oxidation with a measured apparent activation energy of 6.9 ± 1.8 kJ·mol(-1) at a potential of 2.60 V/SHE. DFT simulations indicate that the ClO(4)(-) formation mechanism involves direct oxidation of ClO(3)(-) at the BDD surface to form ClO(3)(•), which becomes activationless at potentials > 0.76 V/SHE. Perchloric acid is then formed via the activationless homogeneous reaction between ClO(3)(•) and OH(•) in the diffuse layer next to the BDD surface. DFT simulations also indicate that the reduction of ClO(3)(•) can occur at radical sites on the BDD surface to form ClO(3)(-) and ClO(2), which limits the overall rate of ClO(4)(-) formation.

Synthesis and luminescence properties of two novel lanthanide (III) perchlorate complexes with bis(benzoylmethyl) sulfoxide and benzoic acid.

Two novel ternary rare earth complexes of Tb(III) and Dy(III) perchlorates with bis(benzoylmethyl) sulfoxide (L) and benzoic acid (L') had been synthesized and characterized by elemental analysis, coordination titration analysis, molar conductivity, IR, TG-DSC, (1)HNMR and UV spectra. The results indicated that the composition of these complexes was REL(5)L'(ClO(4))(2) x nH(2)O (RE = Tb(III), Dy(III); L = C(6)H(5)COCH(2)SOCH(2)COC(6)H(5), L' = C(6)H(5)COO; n = 6,8). The fluorescence spectra illustrated that the ternary rare earth complexes presented stronger fluorescence intensities, longer lifetimes and higher fluorescence quantum efficiencies than the binary rare earth complexes REL(5) x (ClO(4))(3) x 2 H(2)O. After the introduction of the second ligand benzoic acid group, the relative fluorescence emission intensities and fluorescence lifetimes of the ternary complexes REL(5)L'(ClO(4))(2) x nH(2)O (RE = Tb(III), Dy(III)) enhanced more obviously than the binary complexes. This indicated that the presence of both organic ligands bis(benzoylmethyl) sulfoxide and the second ligand benzoic acid could sensitize fluorescence intensities of rare earth ions, and the introduction of benzoic acid group was resulted in the enhancement of the fluorescence properties of the ternary rare earth complexes. The phosphorescence spectra were also discussed.

Cadmium(II) cysteine complexes in the solid state: a multispectroscopic study.

Cadmium(II) cysteinate compounds have recently been recognized to provide an environmentally friendly route for the production of CdS nanoparticles, used in semiconductors. In this article, we have studied the coordination for two cadmium(II) cysteinates, Cd(HCys)(2) x H(2)O (1) and {Cd(HCys)(2) x H(2)O}(2) x H(3)O(+)ClO(4)(-) (2), by means of vibrational (Raman and IR absorption), solid-state NMR ((113)Cd and (13)C), and Cd K- and L(3)-edge X-ray absorption spectroscopy. Indistinguishable Cd K-edge extended X-ray absorption fine structure (EXAFS) and Cd L(3)-edge X-ray absorption near edge structure (XANES) spectra were obtained for the two compounds, showing similar local structure around the cadmium(II) ions. The vibrational spectra show that the cysteine amine group is protonated (NH(3)(+)) and not involved in bonding. The (113)Cd solid-state cross-polarization magic angle spinning NMR spectra showed a broad signal in the approximately 500-700 ppm range, with the peak maximum at about 650 ppm, indicating three to four coordinated thiolate groups. Careful analyses of low-frequency Raman and far-IR spectra revealed bridging and terminal Cd-S vibrational bands. The average Cd-S distance of 2.52 +/- 0.02 A that constantly emerged from least-squares curve-fitting of the EXAFS spectra is consistent with CdS(4) and CdS(3)O coordination. Both structural models yielded reasonable values for the refined parameters, with a slightly better fit for the CdS(3)O configuration, for which the Cd-O distance of 2.27 +/- 0.04 A was obtained. The Cd L(3)-edge XANES spectra of 1 and 2 resembled that of the CdS(3)O model compound and showed that the coordination around Cd(II) ions in 1 and 2 cannot be exclusively CdS(4). The small separation of 176 cm(-1) between the infrared symmetric and antisymmetric COO(-) stretching modes indicates monodentate or strongly asymmetrical bidentate coordination of a cysteine carboxylate group in the CdS(3)O units. The combined results are consistent with a "cyclic/cage" type of structure for both the amorphous solids 1 and 2, composed of CdS(4) and CdS(3)O units with single thiolate (Cd-S-Cd) bridges, although a minor amount of cadmium(II) sites with CdS(3)O(2-3) and CdS(4)O coordination geometries cannot be ruled out.

Electrochemical production of perchlorate as an alternative for the valorization of brines.

In this work, the valorization of brines, with concentrations similar to those produced by reverse osmosis or electrodialysis processes, by electrolysis with diamond anodes is evaluated. To do this, synthetic brines made from solutions of NaCl (with target concentrations ranging from 1.0 to 2.0 M and an additional test at 5.0 M) were used as the raw material for the electrochemical production of perchlorate using commercial electrochemical cells equipped with boron-doped diamond (BDD) anodes. The effect of key parameters on the rate and efficiency of perchlorate production was evaluated. The results show that it is possible to transform more than 80% of the initial chloride concentration into perchlorate, with current efficiencies higher than 70% regardless of the initial concentration of sodium chloride contained in the brine. Moreover, it was observed that both hypochlorite and chlorate were produced almost simultaneously at the beginning of electrolysis, while perchlorate was only produced when a certain value of applied electric charge was passed through the system. The results obtained were essentially independent of the concentration of NaCl, as the high concentrations used in this study avoided mass transfer limitations. Moreover, the specific energy cost of perchlorate production was estimated to range from 26.14 kWh kg-1 (for 2.0 M and 1000 A m-2) to 56.10 kWh kg-1 (for 1.0 M and 2000 A m-2). According to the results obtained, the electrochemical production of perchlorate by BDD electrochemical oxidation stands out as a promising novel technology for the valorization of the brine produced in reverse osmosis or electrodialysis processes.

Perchlorate production by ozone oxidation of chloride in aqueous and dry systems.

Overwhelming evidence now exists that perchlorate is produced through natural processes and can be ubiquitously found at environmentally relevant concentrations in arid and semi-arid locations. A number of potential production mechanisms have been hypothesized and ClO(4)(-) production by ozone oxidation of surface bound Cl(-) was demonstrated. However, no information concerning the impact of concentration, final reaction products distribution, impact of reaction phase, or oxidation of important oxychlorine intermediates has been reported. Using IC-MS-MS analysis and replicate oxidation experiments, we show that exposing aqueous solutions or Cl(-) coated sand or glass surfaces to O(3) (0.96%) generated ClO(4)(-) with molar yields of 0.007 and 0.01% for aqueous Cl(-) solutions and 0.025 and 0.42% for Cl(-) coated sand and glass, respectively. Aqueous solutions of Cl(-) produced less ClO(4)(-) than Cl(-) coated sand or glass as well as a higher ratio of ClO(3)(-) to ClO(4)(-). Reduction of the initial Cl(-) mass resulted in substantially higher molar yields of ClO(4)(-) and ClO(3)(-). In addition, alkaline absorbers that captured gaseous products contained substantial quantities of Cl(-), ClO(3)(-), and ClO(4)(-). Solutions of possible oxychlorine intermediates (OCl(-) and ClO(3)(-)) exposed to O(3) produced only scant amounts of ClO(4)(-) while a ClO(2)(-) solution exposed to O(3) produced substantial molar yields of ClO(4)(-) (4% molar yield). Scanning electron microscopy coupled with energy energy-dispersive X-ray analysis demonstrated a significant loss of Cl(-) and an increase in oxygen on the Cl(-) coated silica sand exposed to O(3). While the experimental conditions are not reflective of natural conditions this work clearly demonstrates the relative potential of Cl(-) precursors in perchlorate production and the likely importance of dry aerosol oxidation over solution phase reactions. It also suggests that ClO(2)(-) may be a key intermediate while ClO(3)(-) and OCl(-) are unlikely to play a significant role.

Investigations to the synthesis of n.c.a. [18F]FClO3 as electrophilic fluorinating agent.

An approach to synthesize the electrophilic fluorinating agent no-carrier-added (n.c.a.) [18F]perchloryl fluoride ([18F]FClO3) in superacidic media in the presence of KClO4 or anhydrous perchloric acid starting from [18F]fluoride was demonstrated in this study. However, the radiochemical yields were low (1-6%) and poorly reproducible. Fluorosulphonic acid proved to be an essential intermediate as revealed by non-radioactive experiments. A key problem in the preparation of [18F]FClO3 is the assumed kinetic inhibition due to the unfavourable stoichiometric ratio of the ClO4 moiety to [18F]HSO3F.

Contact Electrification of Regolith Particles and Chloride Electrolysis: Synthesis of Perchlorates on Mars.

Contact electrification of chloride-impregnated martian regolith particles due to eolian agitation and moisture condensation on coalesced oppositely charged grains may lead to spontaneous electrolysis that generates hypochlorite, chlorite, chlorate, and perchlorate with a concomitant reduction of water to hydrogen. This process is not curtailed even if moisture condenses as ice because chloride ionizes on the surface of ice. Limitations dictated by potentials needed for electrolysis and breakdown electric fields enable estimation of the required regolith grain size. The estimated dimension turns out to be of the same order of magnitude as the expected median size of martian regolith, and a simple calculation yields the optimum rate of perchlorate production. Key Words: Mars oxidants-Perchlorate-Dust electrification-Electrolysis. Astrobiology 16, 811-816.

Energetic co-ordination compounds: synthesis, characterization and thermolysis studies on bis-(5-nitro-2H-tetrazolato-N2)tetraammine cobalt(III) perchlorate (BNCP) and its new transition metal (Ni/Cu/Zn) perchlorate analogues.

Bis-(5-nitro-2H-tetrazolato-N2)tetraammine[cobalt(III)/nickel(III)] perchlorates (BNCP/BNNP) and mono-(5-nitro-H-tetrazolato-N)triammine [copper(II)/zinc(II)] perchlorates (MNCuP/MNZnP) have been synthesized during this work. The synthesis was carried out by addition of carbonato tetraammine metal [Co/Ni/Cu/Zn] nitrate [CTCN/CTNN/CTCuN/CTZnN] to the aqueous solution of sodium salt of 5-nitrotetrazole followed by reaction with perchloric acid. The precursors were synthesized by the reaction of aqueous solution of their respective nitrates with ammonium carbonate at 70 degrees C. The complexes and their precursors were characterized by determining metal and perchlorate content as well as infrared (IR), electron spectra for chemical analysis (ESCA) and X-ray diffraction (XRD) techniques. The TG profiles indicated that BNCP, BNNP and MNCuP are thermally stable up to the temperature of 260-278 degrees C unlike MNZnP (150 degrees C). Sudden exothermic decomposition was observed in case of bis-(5-nitro-2H-tetrazolato-N2)tetraammine cobalt(III) perchlorate, bis-(5-nitro-2H-tetrazolato-N2)tetraammine nickel(III) perchlorate and mono-(5-nitro-H-tetrazolato-N)triammine zinc(II) perchlorate resulting in the severe damage of the sample cup. Sensitivity data indicated that the Co/Ni/Cu complexes are more friction sensitive (3-4.8 kg) than mono-(5-nitro-H-tetrazolato-N)triammine zinc(II) perchlorate (14 kg). The impact sensitivity results of the complexes corresponded to h50% of 30-36 cm.

Dakin-West trick in the design of novel 2-alkyl(aralkyl) derivatives of oxazolo[3,2-a]pyridines.

A series of previously unavailable derivatives of 2-alkyl- and 2-benzylderivatives of oxazolo[3,2-a]pyridines III were obtained via tandem ring opening and ring closure from stable mesoionic 3-acyloxazolo[3,2-a]pyridinium-2-olates I. The key intermediates of this tandem transformation are N-(b-oxoethyl)pyridones-2 II obtained by Dakin-West acylation of (pyridone-2-yl-1)acetic acid. An example of further utilization of this strategy is illustrated by preparation of unknown 2-benzylimidazo[1,2-a]pyridine from the salt I and ammonia.

Synthesis, conformational structure and spectroscopic properties of trans-diazidobis(2,2-dimethyl-1,3-propanediamine)chromium(III) perchlorate.

A new complex trans-anti-[Cr(Me2tn)2(N3)2]ClO4·2H2O, where Me2tn=2,2-dimethyl-1,3-propanediamine was synthesized and characterized, and its molecular structure was established by single-crystal X-ray diffraction at 95K. The complex crystallized in the space group C2/c of the monoclinic system with four mononuclear formula units in a cell of dimensions a=16.600 (3), b=7.709 (2), c=16.865 (3)Å, and ß=99.07 (3)°. The chromium(III) atom was in a distorted octahedral coordination with four N atoms of two chelating Me2tn ligands and two N atoms of the azido group in the trans axial position. The two six-membered rings in the complex adopted only anti chair-chair conformations with respect to each other The important bond lengths are CrN(azide) 2.007 (2), CrN(Me2tn) 2.081 (2), 2.082 (2), NN(azide) 1.184 (2) and 1.156 (2)Å, respectively. The crystal lattice is stabilized by hydrogen bonding interactions among the ClO4(-), hydrate molecule, N3(-), and NH groups of the Me2tn ligand. The ligand field analysis as well as the IR and electronic spectral properties were described.

The bridging bidentate perchlorato group in ReO3(ClO4), ReO3(ClO4Cl2O6 and Sb2Cl6(O)(OH)(ClO4), a vibrational analysis.

Raman and infrared analysis of the new compounds: ReO3(ClO4), an ivory-white solid, and (ClO2)xReO3(ClO4)1+x (x < or = 1), an orange-red chloryl salt, showed that bridging bidentate [ClO4] and terminal ReO3 groups are present in both complexes. Vibrational data on [ClO4] in ReO3(ClO4) were compared to those obtained experimentally and by DFT calculation on a bridging bidentate [ClO4] in Sb2Cl6(O)(OH)(ClO4).

Formation of hazardous inorganic by-products during electrolysis of seawater as a disinfection process for desalination.

From our previous study, an electrochemical process was determined to be a promising tool for disinfection in a seawater desalination system, but an investigation on the production of several hazardous by-products is still required. In this study, a more intensive exploration of the formation patterns of perchlorate and bromate during the electrolysis of seawater was conducted. In addition, the rejection efficiencies of the targeted by-products by membrane processes (microfiltration and seawater reverse osmosis) were investigated to uncover the concentrations remaining in the final product from a membrane-based seawater desalination system for the production of drinking water. On the electrolysis of seawater, perchlorate did not provoke any problem due to the low concentrations formed, but bromate was produced at a much higher level, resulting in critical limitation in the application of the electrochemical process to the desalination of seawater. Even though the formed bromate was rejected via microfiltration and reverse osmosis during the 1st and 2nd passes, the residual concentration was a few orders of magnitude higher than the USEPA regulation. Consequently, it was concluded that the application of the electrochemical process to seawater desalination cannot be recommended without the control of bromate.

Preparation, crystal structure, and thermolysis of phenylenediammonium diperchlorate salts.

Three salts of phenylenediammonium diperchlorate have been prepared and characterized by X-ray crystallography. Their thermal decomposition has been studied by thermogravimetry (TG), differential thermal analysis (DTA), and explosion delay (DE) measurements. The kinetics of thermal decomposition was evaluated by model fitting and isoconversional methods using TG data. The oxidation-reduction reactions near the surface of thermolysing perchlorates may be responsible for the decomposition followed by explosion. The possible pathways of thermolysis have also been proposed.

The synthesis and structure of terpyridine-N-oxide complexes of copper(II) perchlorate.

The co-ordination of a series of terpyridine-N-oxide ligands to the Cu(ii) ion is reported. Addition of two equivalents of ligand results in the formation of the expected 2 : 1 six co-ordinate product, while the addition of one equivalent of ligand allows the isolation of 1 : 1 species if the ligand has a meridonal binding mode. The five complexes isolated were characterised in the solid state by X-ray crystallography while they are studied in solution using EPR, UV-vis spectroscopy and IR spectroscopy.

[Fe(mu-btzmp)2(btzmp)2](ClO4)2: a doubly-bridged 1D spin-transition bistetrazole-based polymer showing thermal hysteresis behaviour.

The reaction of btzmp (1,2-bis(tetrazol-1-yl)-2-methylpropane) with Fe(ClO4)2 generates a 1D polymeric species, [Fe(mu-btzmp)2(btzmp)2](ClO4)2, showing a steep spin transition (T(1/2) / =136 K and T(1/2) / =133 K) with a 3 K thermal hysteresis. The crystal structure at 100 and 200 K reveals that, in contrast to other bistetrazole based spin-transition systems such as [Fe(endi)3](BF4)2 and [Fe(btzp)3](ClO4)2, the present compound has only two ligands bridging the metallic centres, while the other two coordination positions are occupied by two mono-coordinated (non-bridging) btzmp ligands. This peculiarity confers an unprecedented crystal packing in the series of 1D bistetrazole based polymers. The change in spin state is accompanied by an order/disorder transition of the ClO4* counterion. A careful examination of the structural changes occurring upon the spin transition indicates that this order/disorder is most likely affected by the modification of the [tetrazole-centroid]-ND-Fe angle (which is typical of bistetrazole spin-transition materials). Apart from X-ray analysis, also magnetic susceptibility, Mössbauer and UV-vis spectroscopies have been used to characterise the HS and the LS states of [Fe(mu-btzmp)2(btzmp)2](ClO4)2.

Reductive nitrosylation and proton-assisted bridge splitting of a (mu-oxo)dimanganese(III) complex derived from a polypyridine ligand with one carboxamide group.

Aerobic oxidation of the Mn(II) complex [Mn(Papy3)(H2O)](ClO4) (1, PaPy3- is the anion of the designed ligand N,N-bis(2-pyridylmethyl)amine-N-ethyl-2-pyridine-2-carboxamide) in acetonitrile affords the (mu-oxo)dimanganese(III) complex [(Mn(PaPy3))2(mu-O)](ClO4)2 (3) in high yield. The unsupported single oxo bridge between the two high-spin Mn(III) centers in 3 is readily cleaved upon addition of proton sources such as phenol, acetic acid, and benzoic acid, and complexes of the type [Mn(PaPy3)(L)](ClO4) (5, L = PhO-; 6, L = AcO-; 7, L = BzO-) are formed. The basicity of the bridge is evident by the fact that simple addition of methanol to a solution of 3 in acetonitrile affords the methoxide complex [Mn(PaPy3)(OMe)](ClO4) (4). The structures of 3-5 and 7 have been determined. Passage of NO through a solution of 3 in acetonitrile produces the [Mn-NO]6 nitrosyl [Mn(PaPy3)(NO)](ClO4) (2) via reductive nitrosylation. Complexes 4-7 also afford the [Mn-NO]6 nitrosyl 2 upon reaction with NO. In the latter case, the anionic O-based ligands (such as MeO- and PhO-) act as built-in bases and promote reductive nitrosylation of the Mn(III) complexes.

Developing of fluorescence probes based on stilbazolium salts for monitoring free radical polymerization processes. II.

The series of 1-methyl-4-(4-aminostyryl)pyridinium perchlorates was investigated as fluorescent probes for the monitoring of the free radical polymerization progress. The study on the changes in fluorescence intensity and spectroscopic shifts of studied compounds were carried out during thermally initiated polymerization of methyl methacrylate. The purpose of these studies was to find a relationship between the structure of fluorophore and the changes in their fluorescence shape and intensity observed during the monomer conversion into polymer. The probes under the study during the course of polymerization increase their fluorescence intensity at least one order of magnitude. Such increase qualified the tested probes as good fluorescence probes.

Synthesis and X-ray crystal structure of [Ag(phendio)2]ClO4 (phendio = 1,10-phenanthroline-5,6-dione) and its effects on fungal and mammalian cells.

The Cu(II) and Ag(I) complexes, [Cu(phendio)3](ClO4)2 x 4H2O and [Ag(phendio)2]ClO4 (phendio = 1,10-phenanthroline-5,6-dione), are prepared in good yield by reacting phendio with the appropriate metal perchlorate salt. The X-ray crystal structure of the Ag(I) complex shows it to have a pseudo tetrahedral structure. 'Metal-free' phendio and the Cu(II) and Ag(I) phendio complexes strongly inhibit the growth of the fungal pathogen Candida albicans, and are more active than their 1,10-phenanthroline analogues. The simple Ag(I) salts, AgCH3CO2, AgNO3 and AgClO4 x H2O display superior anti-fungal properties compared to analogous simple Cu(II) and Mn(II) salts, suggesting that the nature of the metal ion strongly influences activity. Exposing C. albicans to 'metal-free' phendio, simple Ag(I) salts and [Ag(phendio)2]ClO4 causes extensive, non-specific DNA cleavage. 'Metal-free' phendio and [Ag(phendio)2]ClO4 induce gross distortions in fungal cell morphology and there is evidence for disruption of cell division. Both drugs also exhibit high anti-cancer activity when tested against cultured mammalian cells.