The quenching of excited iodine atoms by oxygen molecules as studied by opto-acoustic spectroscopy

The opto-acoustic spectrum of I₂ in the presence of various quenching gases — NO, O₂, CH₃I, SO₂, C₃H_S, N₂, and He — has been studied. Of these, the I₂/O₂ spectrum is quite different due to the near-resonant energy transfer I(²P$\text{1}\text{2}$) + O₂(³Σ) → I(²P$\text{3}\text{2}$) + O₂(^IΔ), wherein the resistance of the O₂((^IΔ) species to collisional relaxation severely distorts the acoustic signal. The photochemical production of excited ²P$\text{1}\text{2}$ iodine atoms commences at wavelengths considerably longer than the dissociation limit of the I₂B? state.     

Temperature dependence of collisional deactivation of Tl(62P32)

The rate coefficients for the collisional deactivation of Tl(6²P_{$\text{3}\text{2}$}) by several gases has been determined at 300°K. This data is compared with that previously obtained at higher temperatures and the Arrhenius parameters calculated. Both the overall rate coefficients and temperature effects display trends similar to those observed for 1(5²P_{$\text{1}\text{2}$}) relaxation. The deactivation of Tl(6²P_{$\text{3}\text{2}$}) by O₂ is shown to proceed by a process involving an equilibrium with Tl(6²P_{$\text{1}\text{2}$}) and electronically excited oxygen, probably O₂(¹Δ_g).     

Thermal decomposition of magnesian kutnahorite

This work investigates the thermal decomposition of magnesian kutnahorite, which belongs to the dolomite group.The DTA curve measured in static air using a small amount of sample (5.0 mg) is quite different from those published previously. This difference might be due to the effect of a self-generated CO₂ atmosphere.In a CO₂ flow of 100 ml min^?1, magnesian kutnahorite decomposes in four steps. Mg-kutnahorite → CaCO₃ + Mg₂MnO₄ + Mn₃O₄ + MgO → CaCO₃ + CaMnO₃ + MgO → CaCO₃ + CaMnO₃ + Ca₂MnO₄ + MgO → CaMnO₃ + Ca₂MnO₄ + MgO + CaO.However, in a mixed gas flow of CO₂ at 95 ml min^?1 and CO at 5 ml min^?1, it decomposes, like dolomite, in two steps. Mg-kutnahorite → CaCO₃ + (Mg,Mn)$\text{O}\text{-}$ → (Ca, Mn)O + (Mg,Mn)$\text{O}\text{-}$.It has been found that the equilibrium redistribution of Mn between (Ca, Mn)$\text{O}\text{-}$ and (Mg, Mn)$\text{O}\text{-}$ is achieved at the second decomposition step. This is supported by theoretical considerations.Consequently, when the O₂ partial pressure in the atmosphere is low enough to keep Mn in a bivalent state, the Mn bearing dolomite group mineral decomposes in a similar manner to dolomite itself.     

On the decay of the ozonide radical in aqueous alkaline solutions

In flash photolysis of an oxygenated aqueous potassium persulphate solution at pH 12.5 the decay of the ozonide radical has been found to follow $\text{3}\text{2}$ order kinetics which has been explained by reactions O^?₃ + O^? ? 2 O^?₂ and O^?₃ + HO₂ → 2 O₂ + OH^?     

Coulometric titration of iodide and iodine with electrolytically generated hypobromite

Conditions for the quantitative coulometric titration of iodide and iodine with electrolytically generated hypobromite in the presence of borax buffer have been established. Iodide and iodine are oxidized to iodate. The method, with biamperometric indication of the equivalence point, was successfully applied for a wide range of iodide concentrations (6.21–2115μg with reliability intervals of ±0.21–±11μg) and iodine concentrations (24.26–3311μg with reliability intervals of ±0.36–±11.7μg). The determinations are accurate and sensitive even in the presence of large amounts of bromides and chlorides ($\text{Br}{}^{\mathrm{?}}\text{I}{}^{\mathrm{?}}$= 1.2·10⁶ and $\text{C}\text{l}$^?I^?=4.0·10^{3), as well as in the presence of oxidizing agents such as IO₃?, BrO₃? and CrO₄2? ($\text{I}\text{O}$₃?/I₂)=3.2·105, $\text{I}\text{O}$₃?/I₂=3.1·103, $\text{Br}\text{O}$-₃/I₂}=1.1·10⁴ and $\text{Cr}\text{O}$^2-₄/I₂=1.0·10⁴, as was confirmed by statistical tests. The oxidation mechanism under the conditions of coulometric titrations is discussed.     

A photoionization study of the charge transfer reactions: Xe+ + O2 → O+2 + Xe and O+2 + Xe → Xe+ + O2

Photoionization mass spectrometer techniques have been employed to study the charge transfer reactions: Xe⁺ + O₂ → O⁺₂ + Xe and O⁺₂ + Xe → Xe⁺ + O₂. The results show the reaction of Xe⁺(²P_{$\text{3}\text{2}$}) ions with O₂ molecules is much more efficient than the reaction of Xe⁺(²P_{$\text{1}\text{2}$}) ions with O₂ molecules. The charge transfer reaction of O⁺₂ ions with Xe atoms was detected for O⁺₂ ions in the a ⁴Π_u state.     

Proton and carbon nuclear magnetic resonance study on some n- and o-acyl derivatives of monohydroxypyridines

Comparative study on the proton and carbon NMR spectra for a series of $\text{N}$- and $\text{O}$-acyl substituted monohydroxypyridines (C₅H₄NO$\text{R}$: $\text{R}$=-H, -CHO, -COCH₃, -COC(CH₃)₃, -COCF₃, -COC₆H₅, -SO₂CH₃, -SO₂C₆H₄CH₃ is reported. p]Characteristic ¹H, ¹³ NMR and IR spectral features allow simple and unambiguous distinction between the isomeric $\text{N}$- and/or $\text{O}$-acyl-derivatives of 2-, 3- and 4-hydroxypyridines, so that both forms can clearly be identified when tautomeric equilibria occur, since the tautomerism rate is slow on the NMR time scale     

High pressure synthesis and crystal structure of a new series of perovskite-like compounds CMn7O12 (C = Na,Ca, Cd,Sr, La,Nd)

A new series of perovskite-like compounds CMn₇O₁₂ have been synthesized under high pressure and high temperature conditions. C is a large divalent or trivalent cation such as Ca, Cd, Sr, La and Nd. The structures of the quenched materials have been determined from powder X-ray data. They are distortions of the NaMn₇O₁₂ cubic structure. The [C²⁺Mn³⁺₃](Mn³⁺₃Mn⁴⁺)O₁₂ compounds are trigonal ($\text{R}\text{3}$). The C²⁺ and Mn³⁺ as well as the Mn³⁺ and Mn⁴⁺ cations are ordered on the corresponding A and B sites of the perovskite structure, respectively. The [C³⁺Mn³⁺₃] (Mn³⁺₄)O₁₂ compounds are monoclinic ($\text{I}\text{2}\text{m}$). In these compounds the order exists only in the A sites. It is shown that the lower symmetry may be the result of a cooperative Jahn-Teller effect of the Mn³⁺ cations occupying the B sites.     

The importance of spin relaxation in the delayed fluorescence of molecular crystals

Deactivation rate constants of spin-orbital excited Br atoms in the reactions Br(²P_{$\text{1}\text{2}$}) + O₂ → Br(²P_{$\text{3}\text{2}$}) + O₂ (k₁), and Br(²P_{$\text{1}\text{2}$}) + NO → Br(²P_{$\text{3}\text{2}$}) + NO (k₄) have been measured with a photodissociative IBr laser on the electronic transition ²P_{$\text{1}\text{2}$}?²P_{$\text{3}\text{2}$} in the Br atom (λ = 2.7 μm). The values obtained are (6.4 ± 1.8) × 10^?14 cm³ s^?1 and (1.9 ± 0.6) × 10^?12 cm³ s^?1, respectively. Comparison with published data leads to the conclusion that, contrary to a widely accepted point of view, the high rate constants for the quenching of excited halogen atoms are due to resonant energy transfer processes and not to the paramagnetic nature of the quencher.     

Surface-hopping model for near-resonant electronic energy transfer

A surface-hopping model is applied to near-resonant electronic energy transfer in the NFBi and O₂I systems. Multiple surface crossings occur in NFBi at ca. 8 A, corresponding well with measured transfer cross section of 200 A². A Landau-Zener model yields the temperature dependence of the thermally averaged cross section for the laser pumping reaction, O^*₂(a¹Δ) + I(²P_{$\text{3}\text{2}$}) → O₂(X³Σ^?_g) + 1^*(²P_{$\text{1}\text{2}$}).     

Diffusion of oxide ions in LaFeO3 single crystal

The tracer diffusion coefficient, $\text{D1}{}_{\mathrm{<mtext>O</mtext>}}$, of oxide ions in LaFeO₃ single crystal was determined over the temperature range of 900–1100°C by the gas-solid isotopic exchange technique using ¹⁸O as a tracer. For the determination of $\text{D1}{}_{\mathrm{<mtext>O</mtext>}}$, the depth profile of ¹⁸O was measured by means of a secondary ion mass spectrometer (SIMS). The surface exchange reaction was found to be slow and the surface exchange rate constant, k, was determined together with $\text{D1}{}_{\mathrm{<mtext>O</mtext>}}$. It was found that $\text{D1}{}_{\mathrm{<mtext>O</mtext>}}$ at 950°C is proportional to P^?0.58_O2, where P_O2 is an oxygen pressure. The vacancy mechanism was determined for the diffusion of oxide ions from the P_O2 dependence. The vacancy diffusion coefficient, D_V, for LaFeO₃ was nearly the same as that for LaCoO₃ at the same temperature. The activation energy for migration of oxide ion vacancies was 74 kJ · mole^?1 for both oxides.     

C2O(X3Σ−): absolute reaction rates measured by laser induced fluoresence

Absolute rate constants are reported for reactions of C₂O($\text{X}\text{?}$³Σ^?) under pseudo-first-order decay conditions. C₂O is generated by laser photodissociation of C₃O₂ at 266 nm, and detected by dye-laser induced fluorescence on the $\text{A}\text{?}$³Π_i-$\text{X}\text{?}$³Σ^? transition. Rate constants of (433 ± 12), (3.30 ± 0.12) and (1.12 ± 0.05) × 10^?13 cm³ molecule^?1 s^?1 are reported for reactions with NO, O₂ and isobutene. The NO value is approximate due to an apparent dark reaction between NO and C₃O₂. Upper limits of 1 × 10^?14 cm³ molecule^?1 s^?1 are reported for reactions with H₂, CO₂, C₃H₂ and C₂H₄. The C₂O + C₃O₂ reaction does not follow pseudo-first-order decay kinetics. Two explanations are proposed to explain this observation. Results are compared with previous relative rate measurements and are discussed in terms of their relevance to combustion chemistry.     

Hyperfine splitting of 57Fe3+ Mössbauer spectra in diamagnetic host lattices

The Mössbauer spectra of ⁵⁷Fe³⁺ substituted in 0.2 to 0.4 atom % of the octahedral sites in the host lattices Na_0.9Mg_0.45Ti_1.55O₄, TiO₂, Sc₂O₃, LiScO₂ and MgAl₂O₄ have been examined. Hyperfine splittings of the spectra were observed for all cases except Sc₂O₃. In all cases the electron spin resonance spectrum was found, or has been shown to be highly anisotropic as a result of the presence of strong axial or rhombic fields and consequent splitting of the 3d⁵ ground state energy levels. In several cases resolution of the $\text{±}\text{5}\text{2}$ and $\text{±}\text{3}\text{2}$ Mössbauer spectra was observed. Mössbauer spectra of the solid solutions Na_0.9Mg_0.45Ti_1.55O₄Na_0.9Fe_0.9Ti_1.1O₄, LiScO₂LiFeO₂ and TiO₂FeNbO₄ have also been examined.     

Mecanismes d'isomerisation de l'ion C6H5COC3H7+• en phase gazeuse

Isomerisation reactions of 1-phenyl 1-butanone X^+? ($\text{1}$) and five other C₁₀H₁₂O^+? ions are demonstrated to proceed via a single intennediate ($\text{a}$); the H₂O elimination occurs from the tetralol structure ($\text{3}$).     

Reaction of superoxo Co(III) complex with quinones formation of a semiquinone Co(III) complex

The superoxo complex [Co(CN)₅O₂]^3- was found to act as a reducing agent towards quinones. One-electron reduction took place with $\text{o}$-quinones whereas two-electrons reduction with $\text{p}$-quinones. 3,5-Di-$\text{t}$-butyl-$\text{o}$-benzoquinone gave the corresponding semiquinone Co(III) complex quantitatively.     

Oxygenation of 2,6-di-t-butylphenols with superoxo Co(III) complexes

Superoxo Co(III) complexes, [Co(CN)₅O₂][X]₃ where X = Et₃N⁺ and (Ph₃P)₂N⁺, mediate the dioxygen incorporation into 2,6-di-$\text{t}$-butylphenols ($\text{1}$) with the same regioselectivity as that in the base-catalyzed oxygenation of $\text{1}$. The superoxo species acts as a base but is not incorporated into the substrate.     

Interactions magnétiques dans des groupements binucléaires [Fe2O7]8− au sein de Na8Fe2O7

The magnetic interaction in the structural units [Fe₂O₇]^8?, built of two corner-sharing FeO₄ tetrahedra, in Na₈Fe₂O₇ ($\text{Na}{}_2\text{O}\text{Fe}{}_2\text{O}{}_3\text{=}\text{4}\text{1}$) has been studied by magnetic susceptibility measurements (4.2–500 K). An exchange integral $\text{J}\text{K}{}_{\mathrm{<mtext>B</mtext>}}$ of ?37 K is obtained by comparison of the experimental values and the calculated ones using a Heisenberg-Dirac-Van Vleck-type Hamiltonian ? = $\text{?2J}\text{S}\text{?}{}_1\text{S}\text{?}{}_2$. The hypothesis of magnetically isolated [Fe₂O₇]^8? groups is corroborated by Mössbauer spectroscopy between 1.5 and 77 K. The susceptibility measurements of the solid solutions Na₈Fe_2?xM_xO₇ (M = Al, Ga; 0 ≤ x ≤ 0.2 for Al; 0 ≤ x ≤ 2 for Ga) leads to the same conclusion of the existence of isolated Fe³⁺Fe³⁺ pairs in Na₈Fe₂O₇. The type of substitution of Fe by Al or Ga is determined; homonuclear Fe³⁺Fe³⁺ and M³⁺M³⁺ pairs and heteronuclear Fe³⁺M³⁺ pairs are formed.     

Cyanosugars III : The reaction of trimethylsilyl cyanide with keto,epoxy and acetal derivatives of carbohydrates

Reaction of methyl 2-acetamido-4,6-$\text{O}$-benzylidene-2-deoxy-α-$\text{D}$-$\text{ribo}$-hexopyranosid-3-ulose with Me₃SiCN afforded methyl 2-acetamido-4,6-$\text{O}$-benzylidene-3-$\text{C}$-cyano-2-deoxy-3-$\text{O}$-trimethylsilyl-α-$\text{D}$-$\text{allo}$- Reaction of ethyl 4,6-di-$\text{O}$-acetyl-2,3-anhydro-α-$\text{D}$-mannopyranoside with Me₃SiCN gave the corresponding ethyl 4,6-di-$\text{O}$-acetyl-2-$\text{C}$-cyano-2-deoxy-α-$\text{D}$-glucopyranoside. Reaction of methyl 4,6-$\text{O}$-benzylidene-2,3-anhydro-α-$\text{D}$-allopyranoside or methyl 4,6-$\text{O}$-benzylidene-2,3-di-$\text{O}$-tosyl-α-$\text{D}$-glucopyranoside with Me₃SiCN at - 75° or - 50° gave the corresponding methyl 6-$\text{O}$-[(R)-cyano phenyl methyl]-α-$\text{D}$-glyco-pyranosides with high or total regio and stereoselectivity.     

An 57Fe Mössbauer effect study of magnetic ordering in the Fe2O3Cr2O3 system

⁵⁷Fe Mössbauer effect spectra have been obtained as a function of temperature for a series of Fe₂O₃Cr₂O₃ compositions in the range 0.2–75% Fe₂O₃. From 30% of Fe₂O₃ upwards, the dependence of the reduced internal magnetic field $\text{H}{}_{\mathrm{<mtext>eff</mtext>}}\text{(T)}\text{H}{}_{\mathrm{<mtext>eff</mtext>}}\text{(T = 0)}$ on reduced temperature, $\text{T}\text{T}{}_{\mathrm{N}}$, was found to be identical with that for α-Fe₂O₃, indicating the persistence of Fe₂O₃-type ordering over this composition range. For 0.2% of ⁵⁷Fe₂O₃ in Cr₂O₃, the reduced field values fall far below those for α-Fe₂O₃ or Cr₂O₃, and weak coupling of Fe₃⁺ with Cr³⁺ has been inferred.A Morin transition similar to that for α-Fe₂O₃ was not present for samples containing 75% of Fe₂O₃. Quadrupole shifts ? were found to be negative and diminishing between 75 and 30% Fe₂O₃, and positive between 20 and 0.2%. The limiting value at lowest dilution of 0.113 ± 0.010 mm/sec corresponds to a nuclear quadrupole coupling constant e²qQ of 0.45 ± 0.04, approximately half that for α-Fe₂O₃. Cone angles for Fe³⁺ spin vectors in the spin-spiral arrangements for intermediate compositions have been derived, and are similar to, but less extreme than those deduced from neutron diffraction data.     

Singulett-Sauerstoff-induzierte spaltung von spiro[1,8a]dihydroindolizinen

The ¹O₂-induced degradation of spiro[1,8a]dihydroindolizines $\text{1}$ - a new photochromic system - may involve dioxetanes as intermediates giving fulvenylesters $\text{3}$.