Synthesis and hydrolysis of gas-phase lanthanide and actinide oxide nitrate complexes: a correspondence to trivalent metal ion redox potentials and ionization energies

2015 ◽  
Vol 17 (15) ◽  
pp. 9942-9950 ◽  
Author(s):  
Ana F. Lucena ◽  
Célia Lourenço ◽  
Maria C. Michelini ◽  
Philip X. Rutkowski ◽  
José M. Carretas ◽  
...  
Keyword(s):  
Gas Phase ◽  
Metal Ion ◽  
Oxidation States ◽  
Redox Potentials ◽  
Trivalent Metal ◽  
Ionization Energies ◽  
Reduction Potentials ◽  
Hydrolysis Of ◽  
Nitrate Complexes

Gas-phase hydrolysis of lanthanide/actinide MO3(NO3)3−ions relates to the stabilities of the MIVoxidation states, which correlate with IV/III solution reduction potentials and 4th ionization energies.

Correlation of the photoelectron and electronic spectra of thiochromones and thiochromanones with their electrochemical data

1979 ◽  
Vol 57 (6) ◽  
pp. 638-644 ◽  
Author(s):  
Rafik O. Loutfy ◽  
Ian W. J. Still ◽  
Michael Thompson ◽  
Toong S. Leong
Keyword(s):  
Gas Phase ◽  
Substituent Effects ◽  
Spectroscopic Properties ◽  
Oxidation Potential ◽  
Molecular Orbitals ◽  
Absolute Difference ◽  
Linear Free Energy Relationship ◽  
Redox Potentials ◽  
Reduction Potentials ◽  
Oxidation Potentials

The gas phase ionization potentials, electrochemical redox potentials and spectroscopic properties of a series of thiochroman-4-one and thiochromone derivatives have been studied. A dramatic shift in the energies of the lowest vacant and highest occupied molecular orbitals of the parent thiochromanone as a function of the addition of a double bond and/or oxidation of the sulphur atom was observed. This shift in energy of the molecular orbitals was reflected in their spectroscopic characteristics. The lowest singlet (and triplet) state of compounds 1–3 in solution is π,π* in nature, while that of compounds 4–6 is n,π*. These results are best explained in terms of substituent effects on the energetics of the acetophenone moiety. The change in the nature of the lowest excited state from π,π* (1–3) to n,π* (4–6) should result in quite different types of photochemistry for the two series.A linear free-energy relationship between the singlet and triplet energies and the absolute difference between the oxidation and reduction potentials of the two series was found. These correlations have been utilized to estimate the half-wave oxidation potentials of compounds 3–6. A correlation was found to exist between the gas phase ionization potential and the solution electrochemical oxidation potential.

Ion chemistry of second-row transition metals in hydrocarbon flames: cations and anions of Y, Zr, Nb, and Mo

1995 ◽  
Vol 73 (12) ◽  
pp. 2263-2271 ◽  
Author(s):  
Christine C.Y. Chow ◽  
John M. Goodings
Keyword(s):  
Transition Metals ◽  
Gas Phase ◽  
Atmospheric Pressure ◽  
Chemical Ionization ◽  
Negative Ions ◽  
Ion Concentration ◽  
Oxidation States ◽  
Metallic Ions ◽  
Ion Chemistry ◽  
Hydrocarbon Flames

A pair of laminar, premixed, CH4–O2 flames above 2000 K at atmospheric pressure, one fuel-rich (FR) and the other fuel-lean (FL), were doped with ~10−6 mol fraction of the second-row transition metals Y, Zr, Nb, and Mo. Since these hydrocarbon flames contain natural ionization, metallic ions were produced in the flames by the chemical ionization (CI) of metallic neutral species, primarily by H3O+ and OH− as CI sources. Both positive and negative ions of the metals were observed as profiles of ion concentration versus distance along the flame axis by sampling the flames through a nozzle into a mass spectrometer. For yttrium, the observed ions include the YO+•nH2O (n = 0–3) series, and Y(OH)4−. With zirconium, they include the ZrO(OH)+•nH2O (n = 0–2) series, and ZrO(OH)3−. Those observed with niobium were the cations Nb(OH)3+ and Nb(OH)4+, and the single anion NbO2(OH)2−. For molybdenum, they include the cations MoO(OH)2+ and MoO(OH)3+, and the anions MoO3− and MoO3(OH)−. Not every ion was observed in each flame; the FL flame tended to favour the ions in higher oxidation states. Also, flame ions in higher oxidation states were emphasized for these second-row transition metals compared with their first-row counterparts. Some ions written as members of hydrate series may have structures different from those of simple hydrates; e.g., YO+•H2O = Y(OH)2+ and ZrO(OH)+•H2O = Zr(OH)3+, etc. The ion chemistry for the production of these ions by CI in flames is discussed in detail. Keywords: transition metals, ions, flame, gas phase, negative ions.

Metal Ion Catalysis in the Hydrolysis of Potassium Ethyl Oxalate

Nature ◽  
1964 ◽  
Vol 204 (4964) ◽  
pp. 1189-1190
Author(s):  
ROBERT W. HAY ◽  
NEIL J. WALKER
Keyword(s):  
Metal Ion ◽  
Metal Ion Catalysis ◽  
Hydrolysis Of

Metal ion effects on the acid hydrolysis of pyrophosphate

1964 ◽  
Vol 26 (8) ◽  
pp. 1415-1420 ◽  
Author(s):  
J.M. Rainey ◽  
M.M. Jones ◽  
W.L. Lockhart
Keyword(s):  
Acid Hydrolysis ◽  
Metal Ion ◽  
Ion Effects ◽  
Metal Ion Effects ◽  
Hydrolysis Of
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