Oxidative dehydrogenation of propane over V2O5/MoO3/Al2O3 and V2O5/Cr2O3/Al2O3: structural characterization and catalytic function

The structure and catalytic properties of binary dispersed oxide structures prepared by sequential deposition of VO(x) and MoO(x) or VO(x) and CrO(x) on Al(2)O(3) were examined using Raman and UV-visible spectroscopies, the dynamics of stoichiometric reduction in H(2), and the oxidative dehydrogenation of propane. VO(x) domains on Al(2)O(3) modified by an equivalent MoO(x) monolayer led to dispersed binary structures at all surface densities. MoO(x) layers led to higher reactivity for VO(x) domains present at low VO(x) surface densities by replacing V-O-Al structures with more reactive V-O-Mo species. At higher surface densities, V-O-V structures in prevalent polyvanadates were replaced with less reactive V-O-Mo, leading to lower reducibility and oxidative dehydrogenation rates. Raman, reduction, and UV-visible data indicate that polyvanadates predominant on Al(2)O(3) convert to dispersed binary oxide structures when MoO(x) is deposited before or after VO(x) deposition; these structures are less reducible and show higher UV-visible absorption energies than polyvanadate structures on Al(2)O(3). The deposition sequence in binary Mo-V catalysts did not lead to significant differences in structure or catalytic rates, suggesting that the two active oxide components become intimately mixed. The deposition of CrO(x) on Al(2)O(3) led to more reactive VO(x) domains than those deposited on pure Al(2)O(3) at similar VO(x) surface densities. At all surface densities, the replacement of V-O-Al or V-O-V structures with V-O-Cr increased the reducibility and catalytic reactivity of VO(x) domains; it also led to higher propene selectivities via the selective inhibition of secondary C(3)H(6) combustion pathways, prevalent in VO(x)-Al(2)O(3), and of C(3)H(8) combustion routes that lead to low alkene selectivities on CrO(x)-Al(2)O(3). VO(x) and CrO(x) mix significantly during synthesis or thermal treatment to form CrVO(4) domains. The deposition sequence, however, influences catalytic selectivities and reduction rates, suggesting the retention of some of the component deposited last as unmixed domains exposed at catalyst surfaces. These findings suggest that the reduction and catalytic properties of active VO(x) domains can be modified significantly by the formation of binary dispersed structures. VO(x)-CrO(x) structures, in particular, lead to higher oxidative dehydrogenation rates and selectivities than do VO(x) domains present at similar surface densities on pure Al(2)O(3) supports.     

In situ UV-vis-NIR diffuse reflectance and Raman spectroscopy and catalytic activity studies of propane oxidative dehydrogenation over supported CrO3/ZrO2 catalysts

The molecular structures, oxidation states, and reactivity of 3 and 6% CrO3/ZrO2 catalysts prepared by incipient wetness impregnation were examined under different conditions. The in situ Raman spectroscopic studies under dehydrated conditions reveal that the 3 and 6% CrO3/ZrO2 catalysts possess equal amounts of monochromate and polychromate species. Consequently, monolayer coverage on this ZrO2 support is about 3% CrO3. The 6% CrO3/ZrO2 possesses an additional Raman band due to Cr2O3 crystals corresponding to the remaining 3% CrO3. Furthermore, during reaction conditions the polychromate species is preferentially reduced, the monochromate species are slightly affected, and the Cr2O3 crystals are not affected. The in situ UV-vis-NIR diffuse reflectance spectroscopy results reveal that under steady-state reaction conditions the extent of reduction and edge energy position of surface Cr6+ cations increase with an increase in reduction environment for the 3 and 6% CrO3/ZrO2 samples. Propane oxidative dehydrogenation (ODH) studies reveal that the catalytic activity expressed in moles of propane converted per gram catalyst per second is similar for the two catalysts, which is consistent with equal amounts of molecularly dispersed chromia present. The turnover frequency for the 6% CrO3/ZrO2 catalyst is, however, smaller than that for the 3% CrO3/ZrO2 sample due to the presence of Cr2O3 crystals, which are relatively inactive for propane ODH. For this catalytic system and for the experimental conditions used, propene, CO, and CO2 are primary products. Furthermore, the 33-39% propene selectivity is not affected by the C3H8/O2 ratio for both catalysts. Structure-reactivity studies suggest that the molecularly dispersed species are present in equal amounts in the 3 and 6% CrO3/ZrO2 samples as Cr6+ monochromate and polychromate species are the most effective catalytic active sites taking part in the propane ODH reaction.     

Quantitative determination of the speciation of surface vanadium oxides and their catalytic activity

A quantitative method based on UV-vis diffuse reflectance spectroscopy (DRS) was developed that allows determination of the fraction of monomeric and polymeric VO(x) species that are present in vanadate materials. This new quantitative method allows determination of the distribution of monomeric and polymeric surface VO(x) species present in dehydrated supported V(2)O(5)/SiO(2), V(2)O(5)/Al(2)O(3), and V(2)O(5)/ZrO(2) catalysts below monolayer surface coverage when V(2)O(5) nanoparticles are not present. Isolated surface VO(x) species are exclusively present at low surface vanadia coverage on all the dehydrated oxide supports. However, polymeric surface VO(x) species are also present on the dehydrated Al(2)O(3) and ZrO(2) supports at intermediate surface coverage and the polymeric chains are the dominant surface vanadia species at monolayer surface coverage. The propane oxidative dehydrogenation (ODH) turnover frequency (TOF) values are essentially indistinguishable for the isolated and polymeric surface VO(x) species on the same oxide support, and are also not affected by the Br?nsted acidity or reducibility of the surface VO(x) species. The propane ODH TOF, however, varies by more than an order of magnitude with the specific oxide support (ZrO(2) > Al(2)O(3) > SiO(2)) for both the isolated and polymeric surface VO(x) species. These new findings reveal that the support cation is a potent ligand that directly influences the reactivity of the bridging V-O-support bond, the catalytic active site, by controlling its basic character with the support electronegativity. These new fundamental insights about polymerization extent of surface vanadia species on SiO(2), Al(2)O(3), and ZrO(2) are also applicable to other supported vanadia catalysts (e.g., CeO(2), TiO(2), Nb(2)O(5)) as well as other supported metal oxide (e.g., CrO(3), MoO(3), WO(3)) catalyst systems.     

Synthesis, structure, and catalytic reactivity of isolated V5+-Oxo species prepared by sublimation of VOCl3 onto H-ZSM5

Isolated and uniform V(5+)-oxo species were grafted onto H-ZSM5 at V/Al(f) ratios of 0.2-1 via sublimation of VOCl(3) precursors. These methods avoid the restricted diffusion of solvated oligomers in aqueous exchange, which leads to poorly dispersed V(2)O(5) at external zeolite surfaces. Sublimation methods led to stable and active V-ZSM5 catalysts for oxidative dehydrogenation (ODH) reactions; they led to an order of magnitude increase in primary C(2)H(6) ODH rates compared with impregnated ZSM5 catalysts at similar V/Al(f) ratios and showed similar activity to impregnated VO(x)/Al(2)O(3). The structure of grafted V(5+)-oxo species was probed using spectroscopic and titration methods. Infrared spectra in the OH region and isotopic exchange of D(2) with residual OH groups showed that exposure to VOCl(3(g)) at 473 K led to stoichiometric replacement of H(+) by each (VOCl(2))(+) species. Raman spectra supported by Density Functional Theory electronic structure and frequency calculations showed that, at V/Al(f) < 0.5, hydrolysis and subsequent dehydration led to the predominant formation of (VO(2))(+) species coordinated to one Al site with single-site catalytic behavior (0.7-0.9 x 10(-3) mol C(2)H(4) V(-1) s(-1), 673 K). At higher V/Al(f) ratios, simulation of extended X-ray absorption fine structure spectra indicated that V(2)O(4)(2+) dimers coexisted with VO(2)(+) monomers and led to an enhancement in ODH rates as a result of bridging V-O-V (1.3 x 10(-3) mol C(2)H(4) V(-1) s(-1)). These V(5+)-oxo species form via initial reactions between VOCl(3(g)) and OH groups to form HCl((g)), hydrolysis of grafted (VOCl(2))(+) to form HCl((g)) and (VO(OH)(2))(+), and intramolecular and intermolecular condensation to form monomers and dimers, respective with the concurrent evolution of H(2)O. Raman and X-ray spectroscopies did not detect crystalline V(2)O(5) at V/Al(f) ratios of 0.2-1, but V(2)O(5) crystals were apparent in samples prepared by impregnation or physical mixtures of V(2)O(5)/H-ZSM5. Framework Al atoms and zeolite crystal structures are maintained during VOCl(3) treatment and subsequent hydrolysis; (27)Al and (29)Si MAS NMR showed that these synthetic protocols removes <10% of the framework Al atoms (Al(f)).     

Reactions of superoxo and oxo metal complexes with aldehydes. Radical-specific pathways for cross-disproportionation of superoxometal ions and acylperoxyl radicals

The aquachromyl(IV) ion, Cr(aq)O(2+), reacts with acetaldehyde and pivaldehyde by hydrogen atom abstraction and, in the presence of O(2), produces acylperoxyl radicals, RC(O)OO(*). In the next step, the radicals react with Cr(aq)OO(2+), a species accompanying Cr(aq)O(2+) in our preparations. The rate constant for the Cr(aq)OO(2+)/CH(3)C(O)OO(*) cross reaction, k(Cr) = 1.5 x 10(8) M(-1) s(-1), was determined by laser flash photolysis. The evidence points to radical coupling at the remote oxygen of Cr(aq)OO(2+), followed by elimination of O(2) and formation of CH(3)COOH and Cr(V)(aq)O(3+). The latter disproportionates and ultimately yields Cr(aq)(3+) and HCrO(4)(-). No CO(2) was detected. The Cr(aq)OO(2+)/C(CH(3))(3)C(O)OO(*) reaction yielded isobutene, CO(2), and Cr(aq)(3+), in addition to chromate. In the suggested mechanism, the transient Cr(aq)OOOO(O)CC(CH(3))(3)(2+) branches into two sets of products. The path leading to chromate resembles the CH(3)C(O)OO(*) reaction. The other products arise from an unprecedented intramolecular hydrogen transfer from the tert-butyl group to the CrO entity and elimination of CO(2) and O(2). A portion of C(CH(3))(3)C(O)OO(*) was captured by (CH(3))(3)COO(*), which was in turn generated by decarbonylation of acyl radicals and oxygenation of tert-butyl radicals so formed.     

Novel Pathways in the Reactions of Superoxometal Complexes

The reaction of a 1:1 mixture of (H(2)O)(5)Cr((16)O(2))(2+) and (H(2)O)(5)Cr((18)O(2))(2+) at pH 1 did not yield measurable amounts of (16)O(18)O. This result rules out a Russell-type mechanism (2(H(2)O)(5)CrO(2)(2+) --> 2(H(2)O)(5)CrO(2+) + O(2)) for the bimolecular decomposition reaction. Evidence is presented in support of unimolecular (S(H)1) and bimolecular (S(H)2) homolyses as initial steps in the decomposition of (H(2)O)(5)CrO(2)(2+) in strongly acidic solutions (pH 相似文献   

Reaction of a superoxochromium(III) ion with nitrogen monoxide: kinetics and mechanism.

The kinetics of the rapid reaction between Cr(aq)OO(2+) and NO were determined by laser flash photolysis of Cr(aq)NO(2+) in O(2)-saturated acidic aqueous solutions, k = 7 x 10(8) M(-1) s(-1) at 25 degrees C. The reaction produces an intermediate, believed to be NO(2), which was scavenged with ([14]aneN(4))Ni(2+). With limiting NO, the Cr(aq)OO(2+)/NO reaction has a 1:1 stoichiometry and produces both free NO(3)(-) and a chromium nitrato complex, Cr(aq)ONO(2)(2+). In the presence of excess NO, the stoichiometry changes to [NO]/[Cr(aq)OO(2+)] = 3:1, and the reaction produces close to 3 mol of nitrite/mol of Cr(aq)OO(2+). An intermediate, identified as a nitritochromium(III) ion, Cr(aq)ONO(2+), is a precursor to a portion of free NO(2)(-). In the proposed mechanism, the initially produced peroxynitrito complex, Cr(aq)OONO(2+), undergoes O-O bond homolysis followed by some known and some novel chemistry of Cr(aq)O(2+) and NO(2). The reaction between Cr(aq)O(2+) and NO generates Cr(aq)ONO(2+), k > 10(4) M(-1) s(-1). Cr(aq)OO(2+) reacts with NO(2) with k = 2.3 x 10(8) M(-1) s(-1).     

Application of xylenol orange to the separation of metal ions on amberlyst A-26 macroreticular anion-exchange resin

The possibility of using a sulphonated aromatic organic complexing agent-Xylenol Orange-for separation of metal ions on the macroreticular anion-exchanger Amberlyst A-26 has been investigated. The dependence of retention on pH was determined by the batch method for Al(3+), Cr(3+), Mn(3+), Fe(3+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Ga(3+), Rh(3+) Cd(2+), In(3+), Ir(3+), and Pb(2+). The selectivity differences make possible the separation of some of these metal ions. The following mixtures, of practical importance, have been separated: Al(3+)-In(3+), Ga(3+)-In(3+) Zn(2+)-In(3+), Cu(2+)-Mn(2+), in various ratios. The method has been applied to analysis of Ga-In alloy.     

Studies on metallochromic indicators-III Hematoxylin and hematein

The use of hematoxylin and hematein as metallochromic indicators in direct EDTA titration of Zr(4+), Th(4+), Bi(3+), VO(+), Ga(3+), In(3+), Al(3+), Pb(+), Zn(2+), Mn(2+), Cd(2+), Cu(2+), Ni(2+), Co(2+), Mg(2+), and a few rare earths is described. Aluminium is titrated directly in presence of acetate buffer, lactic or glycoliic acid being used as auxiliary complexing agent. Mixtures of two metal ions can be titrated if one is Bi(3+) and the other Al(3+), Pb(2+), Zn(2+), Cu(2+), Cd(2+), La(3+), Ce(3+), Pr(3+), Nd(3+), Sm(3+), Gd(3+) or Er(3+). Aluminium alloys can be analysed via EDTA titrations, with these indicators.     

Rapid cross-disproportionation between superoxometal ions and acylperoxyl radicals

A superoxochromium complex Cr(aq)OO(2+) reacts with acetylperoxyl radicals, CH(3)C(O)OO(*), with a rate constant of 1.49 x 10(8) M(-1) s(-1). The kinetics were determined by laser flash photolysis, using an organocobalt complex as a radical precursor and ABTS(*-) as a kinetic probe. The initial step is believed to involve radical coupling at the remote oxygen of Cr(aq)OO(2+), followed by elimination of O(2) and formation of CH(3)COOH and Cr(V)(aq)O(3+). The latter disproportionates and ultimately yields Cr(aq)(3+) and HCrO(4)(-).     

Microwave-assisted solvothermal synthesis and characterization of metastable LiFe(1-x)(VO)(x)PO4 cathodes

Vanadyl ion substituted LiFePO(4) cathodes of the form LiFe(1-x)(VO)(x)PO(4) for 0 ≤ x ≤ 0.25 have been synthesized by a rapid microwave-solvothermal process at <300 °C within 10 min. Clear evidence of vanadyl ion substitution is demonstrated, despite a large size difference between Fe(2+) and (VO)(2+), by characterizing the products structurally, spectroscopically, and electrochemically. The vanadyl ion substitution is accompanied by the formation of iron vacancies in the lattice and Fe(3)O(4) impurity phase, which increases with increasing (VO)(2+) substitution for Fe(2+) and could be removed with a magnetic stir bar. The formation of iron vacancies, along with the oxidation of some Fe(2+) to Fe(3+) to maintain charge neutrality, results in a decrease in the unit cell volume with increasing x despite the substitution of larger (VO)(2+) for Fe(2+). Charge-discharge data of the vanadyl ion substituted samples suggest suppression of the two-phase plateau behavior that is characteristic of LiFePO(4). Electrochemical data collected without any carbon coating reveal that the capacity and rate capability decreases, but the capacity retention improves with (VO)(2+) substitution.     

Optical Switching in VO2 Thin Films

Vanadium dioxide thin films have been deposited from vanadium alkoxides VO(OR)3. An amorphous film is formed that transforms into crystalline VO2 upon heating at 500°C under a reducing atmosphere. Optically transparent VO2 thin films are then obtained that exhibit both electrical and optical switching around 70°C. The switching temperature together with the shape of the hysteresis loop can be modified by doping VO2 films with foreign cations. Doped MxVO2 (M = W6+, Nb5+, Ti4+, Cr3+ or Al3+) thin films have been prepared under the same conditions by mixing the vanadium alkoxide and a metal salt in an alcoholic solution. The switching temperature decreases when the film is doped with high-valent cations (W6+) and increases with low-valent cations (Al3+, Cr3+). The transition temperature first decreases and then increases when TiIV is added to the VO2 film while the width of the hysteresis loop is significantly reduced.     

Synthesis and characterization of iron(III)-substituted, dimeric polyoxotungstates, [Fe(4)(H(2)O)(10)(beta-XW(9)O(33))(2)](n-) (n = 6, X = As(III), Sb(III); n = 4, X = Se(IV), Te(IV))

Interaction of the lacunary [alpha-XW(9)O(33)](9-) (X = As(III), Sb(III)) with Fe(3+) ions in acidic, aqueous medium leads to the formation of dimeric polyoxoanions, [Fe(4)(H(2)O)(10)(beta-XW(9)O(33))(2)](6-) (X = As(III), Sb(III)) in high yield. X-ray single-crystal analyses were carried out on Na(6)[Fe(4)(H(2)O)(10)(beta-AsW(9)O(33))(2)] x 32H(2)O, which crystallizes in the monoclinic system, space group C2/m, with a = 20.2493(18) A, b = 15.2678(13) A, c = 16.0689(14) A, beta = 95.766(2) degrees, and Z = 2; Na(6)[Fe(4)(H(2)O)(10)(beta-SbW(9)O(33))(2)] x 32H(2)O is isomorphous with a = 20.1542(18) A, b = 15.2204(13) A, c = 16.1469(14) A, and beta = 95.795(2) degrees. The selenium and tellurium analogues are also reported, [Fe(4)(H(2)O)(10)(beta-XW(9)O(33))(2)](4-) (X = Se(IV), Te(IV)). They are synthesized from sodium tungstate and a source of the heteroatom as precursors. X-ray single-crystal analysis was carried out on Cs(4)[Fe(4)(H(2)O)(10)(beta-SeW(9)O(33))(2)] x 21H(2)O, which crystallizes in the triclinic system, space group P macro 1, with a = 12.6648(10) A, b = 12.8247(10) A, c = 16.1588(13) A, alpha = 75.6540(10) degrees, beta = 87.9550(10) degrees, gamma = 64.3610(10) gamma, and Z = 1. All title polyanions consist of two (beta-XW(9)O(33)) units joined by a central pair and a peripheral pair of Fe(3+) ions leading to a structure with idealized C(2h) symmetry. It was also possible to synthesize the Cr(III) derivatives [Cr(4)(H(2)O)(10)(beta-XW(9)O(33))(2)](6-) (X = As(III), Sb(III)), the tungstoselenates(IV) [M(4)(H(2)O)(10)(beta-SeW(9)O(33))(2)]((16)(-)(4n)-) (M(n+) = Cr(3+), Mn(2+), Co(2+), Ni(2+), Zn(2+), Cd(2+), and Hg(2+)), and the tungstotellurates(IV) [M(4)(H(2)O)(10)(beta-TeW(9)O(33))(2)]((16-4n)-) (M(n+) = Cr(3+), Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), and Hg(2+)), as determined by FTIR. The electrochemical properties of the iron-containing species were also studied. Cyclic voltammetry and controlled potential coulometry aided in distinguishing between Fe(3+) and W(6+) waves. By variation of pH and scan rate, it was possible to observe the stepwise reduction of the Fe(3+) centers.     

Highly sensitive, selective, and rapid fluorescence Hg2+ sensor based on DNA duplexes of poly(dT) and graphene oxide

Coupling T base with Hg(2+) to form stable T-Hg(2+)-T complexes represents a new direction in detection of Hg(2+). Here a graphene oxide (GO)-based fluorescence Hg(2+) analysis using DNA duplexes of poly(dT) that allows rapid, sensitive, and selective detection is first reported. The Hg(2+)-induced T(15)-(Hg(2+))(n)-T(15) duplexes make T(15) unable to hybridize with its complementary A(15) labelled with 6'-carboxyfluorescein (FAM-A(15)), which has low fluorescence in the presence of GO. On the contrary, when T(15) hybridizes with FAM-A(15) to form double-stranded DNA because of the absence of Hg(2+), the fluorescence largely remains in the presence of GO. A linear range from 10 nM to 2.0 μM (R(2) = 0.9963) and a detection limit of 0.5 nM for Hg(2+) were obtained under optimal experimental conditions. Other metal ions, such as Al(3+), Ag(+), Ca(2+), Ba(2+), Mg(2+), Zn(2+), Mn(2+), Co(2+), Pb(2+), Ni(2+), Cu(2+), Cd(2+), Cr(3+), Fe(2+), and Fe(3+), had no significant effect on Hg(2+) detection. Moreover, the sensing system was used for the determination of Hg(2+) in river water samples with satisfactory results.     

NO2 adsorption on BaO/Al2O3: the nature of nitrate species

Temperature programmed desorption, infrared spectroscopy, and (15)N solid state NMR spectroscopy were used to characterize the nature of the nitrate species formed on Al(2)O(3) and BaO/Al(2)O(3) NO(x) storage/reduction materials. Two distinctly different nitrate species were found: surface nitrates that are associated with a monolayer BaO on the alumina support, and a bulk-like nitrate that forms on this thin BaO layer. The surface nitrates desorb as NO(2) at lower temperatures than do the bulk-like nitrates, which decompose as NO+O(2) at higher temperatures. The amount of NO(x) stored in the monolayer nitrate is proportional to the surface area of the catalyst, while that in the bulk nitrate increases with BaO coverage.     

Preparation of USY zeolite VOx supported catalysts from V(AcAc)3 and NH4VO3. Catalytic properties for the dehydrogenation of n-butane in oxygen-free atmosphere

The preparation of different samples of vanadia supported on ultrastable zeolite (VO(x)/USY) is discussed. The samples were prepared in order to obtain highly dispersed V-species, avoiding the formation of crystalline vanadia and the destruction of the zeolite framework. Two methods were employed for preparing VO(x)/USY samples: an organic route using V(AcAc)3 and an inorganic route using NH4VO3. The characterization of the samples was performed with XRD, TPR, NH3-TPD, and N2 isotherms. From these results it is concluded that when VO(x) is supported on the surface of USY from acidic aqueous solution of ammonium metavanadate, the destruction of the zeolite framework is accomplished. For higher pH values in the impregnating solution, undesired V2O5 is formed on the USY surface. On the other hand, VO(x)/USY prepared from the organic precursor shows no destruction of the USY structure. In addition, highly dispersed VO(x) are formed, though for relatively high V loadings (6%) an obstruction of the zeolite windows takes place. The samples are tested as catalysts for gas phase dehydrogenation of n-butane to olefins. The catalysts prepared from NH4VO3 are almost inactive for the reaction. On the other hand, both samples prepared from V(AcAc)3 present initial conversion levels in the 8-12% range. However, the selectivity depends on the V loading, the catalysts with 6% loading being the most selective (75%). The catalytic patterns of the samples (activity and selectivity) are in agreement with the physicochemical features of the VO(x)/USY surface.     

Acid-catalyzed oxidation of iodide ions by superoxo complexes of rhodium and chromium

Superoxometal complexes L(H(2)O)MOO(2+) (L = (H(2)O)(4), (NH(3))(4), or N(4)-macrocycle; M = Cr(III), Rh(III)) react with iodide ions according to the stoichiometry L(H(2)O)MOO(2+) + 3I(-) + 3H(+) --> L(H(2)O)MOH(2+) + 1.5I(2) + H(2)O. The rate law is -d[L(H(2)O)MOO(2+)]/dt = k [L(H(2)O)MOO(2+)][I(-)][H(+)], where k = 93.7 M(-2) s(-1) for Cr(aq)OO(2+), 402 for ([14]aneN(4))(H(2)O)CrOO(2+), and 888 for (NH(3))(4)(H(2)O)RhOO(2+) in acidic aqueous solutions at 25 degrees C and 0.50 M ionic strength. The Cr(aq)OO(2+)/I(-) reaction exhibits an inverse solvent kinetic isotope effect, k(H)()2(O)/k(D)2(O) = 0.5. In the proposed mechanism, the protonation of the superoxo complex precedes the reaction with iodide. The related Cr(aq)OOH(2+)/I(-) reaction has k(H)2(O)/k(D)2(O) = 0.6. The oxidation of (NH(3))(5)Rupy(2+) by Cr(aq)OO(2+) exhibits an [H(+)]-dependent pathway, rate = (7.0 x 10(4) + 1.78 x 10(5)[H(+)])[Ru(NH(3))(5)py(2+)][Cr(aq)OO(2+)]. Diiodine radical anions, I(2)(*)(-), reduce Cr(aq)OO(2+) with a rate constant k = 1.7 x 10(9) M(-1) s(-1).     

Oxidative homolysis of a nitrosylchromium complex

Metal(III)-polypyridine complexes [M(NN)(3)](3+) (M = Ru or Fe; NN = bipyridine (bpy), phenanthroline (phen), or 4,7-dimethylphenanthroline (Me(2)-phen)) oxidize the nitrosylpentaaquachromium(III) ion, [Cr(aq)NO](2+), with an overall 4:1 stoichiometry, 4 [Ru(bpy)(3)](3+) + [Cr(aq)NO](2+) + 2 H(2)O --> 4 [Ru(bpy)(3)](2+) + [Cr(aq)](3+) + NO(3)(-) + 4 H(+). The kinetics follow a mixed second-order rate law, -d[[M(NN)(3)](3+)]/dt = nk[[M(NN)(3)](3+)][[Cr(aq)NO](2+)], in which k represents the rate constant for the initial one-electron transfer step, and n = 2-4 depending on reaction conditions and relative rates of the first and subsequent steps. With [Cr(aq)NO](2+) in excess, the values of nk are 283 M(-1) s(-1) ([Ru(bpy)(3)](3+)), 7.4 ([Ru(Me(2)-phen)(3)](3+)), and 5.8 ([Fe(phen)(3)](3+)). In the proposed mechanism, the one-electron oxidation of [Cr(aq)NO](2+) releases NO, which is further oxidized to nitrite, k = 1.04x10(6) M(-1) s(-1), 6.17x10(4), and 1.12x10(4) with the three respective oxidants. Further oxidation yields the observed nitrate. The kinetics of the first step show a strong correlation with thermodynamic driving force. Parallels were drawn with oxidative homolysis of a superoxochromium(III) ion, [Cr(aq)OO](2+), to gain insight into relative oxidizability of coordinated NO and O(2), and to address the question of the "oxidation state" of coordinated NO in [Cr(aq)NO](2+).     

New masking procedure for selective complexometric determination of copper(II)

A study has been made of a new masking procedure for highly selective complexometric determination of copper(II), based on decomposition of the copper-EDTA complex at pH 5-6. Among the various combinations of masking agents tried, ternary masking mixtures comprising a main complexing agent (thiourea), a reducing agent (ascorbic acid) and an auxiliary complexing agent (thiosemicarbazide or a small amount of 1,10-phenanthroline or 2,2'-dipyridyl) have been found most suitable. An excess of EDTA is added and the surplus EDTA is back-titrated with lead (or zinc) nitrate with Xylenol Orange as indicator (pH 5-6). A masking mixture is then added to decompose the copper-EDTA complex and the liberated EDTA is again back-titrated with lead (or zinc) nitrate. The following cations do not interfere: Ag(+), Hg(2+), Pb(2+), Ni(2+), Bi(3+), As(3+), Al(3+), Sb(3+), Sn(4+), Cd(2+), Co(2+), Cr(3+) and moderate amounts of Fe(3+) and Mn(2+). The notable feature is that consecutive determination of Hg(2+) and Cu(2+) can be conveniently carried out in the presence of other cations.