Formation of triphenylmethyl cation during the photolysis of phenylazotriphenyl methane: a laser flash photolysis study

The photolysis of phenylazotriphenyl methane (PAT) in dichloromethane and acetonitrile solution at λ_inc = 347nm and at 23°C results in the formation of triphenyl methyl (trityl) radicals and trityl ions. The quantum yields in dichloromethane solution are Φ(Ph₃C^•) = 0·060 and Φ(Ph₃C⁺) = 0·004. Trityl ions are assumed to be formed by electron transfer between radicals formed by the photodecomposition of PAT. The yield of trityl ions is significantly increased upon irradiation of PAT solutions containing also an onium salt (N-ethoxy-2-methyl pyridinium hexafluorophosphate; (EMP⁺PF₆^-). This is due to the oxidation of trityl radicals by EMP⁺ ions. Trityl ions generated in this way were found to be capable of initiating the cationic polymerization of cyclohexene oxide. © 1998 SCI.     

A chemically regenerative redox fuel cell

A novel chemically regenerative redox fuel cell is described. The electrode reactions are based on the following redox reactions: cathodic reaction: anodic reaction: VO ₂ ⁺ +2H⁺+e VO²⁺+H₂O (E ₀ +1V), SiW₁₂O ₄₀ ^5– SiW₁₂O ₄₀ ^4– +e (E ₀ 0V). Regeneration of the oxidant by direct oxidation with O₂ was achieved by using the soluble heteropoly acid catalysts, H₃PMo₁₂O₄₀ or H₅PMo₁₀V₂O₄₀, whereas regeneration of the tungstosilicic acid, H₃SiW₁₂O₄₀, was accomplished by direct reduction with H₂ utilizing small amounts of Pt, Pd, Rh, Ru or the soluble Pd-4, 4, 4, 4'-tetrasulphophthalocyanine complex as catalysts. Some aspects of the regeneration kinetics and their influence on the overall performance of the redox fuel cell are discussed.     

The redox mechanism of the chelate-catalysed oxygen cathode

The electro-reduction of oxygen is effectively catalysed by metal chelates of the N4-type. The mechanism of this process has been found to be a modified redox catalysis. O₂ molecules and the products of their reaction, at least up to H₂O₂, remain strongly co-ordinated to the central metal ion of the chelates XMe^II. The potential-determining step, which regenerates the reduced form, is the following: (XMe^III...O₂H)⁺+H⁺+ 2eXMe^II+H₂O₂.H₂O₂ is further decomposed via the catalase action of the electrocatalyst. The mechanism is confirmed by experimental results with iron phthalocyanine (FePc) and cobalt-dibenzotetraazaannulene (CoTAA) as a O₂-slurry electrode at various O₂ pressures. The latter shows anodic reaction-limited currents, which seem to involve also oxygen-containing intermediates. The implication of the presented mechanism in regard to other electrochemical processes is discussed briefly.     

The aerobic and peroxide-induced coupling of aqueous thiols—II. Reaction mechanisms,model analysis,and a comparison of the model and experimental results

Kinetic results of the preceeding paper are used to formulate the most probable reaction mechanisms for the peroxide-induced and aerobic coupling of aqueous thiols. Parameters in the proposed mechanisms are evaluated for n-propylthiol using the results of independent measurements. A remarkably good agreement is achieved between the model and experimental results.The peroxide reaction, which is not affected by either copper ion or radical scavengers, is shown to be a nucleophilic substitution (S_N 2) reaction which proceeds by a two-step mechanism as follows: RS⁻ + H₂O₂

RSOH + OH⁻ rate-determining RS⁻ + RSOH → RSSR + OH⁻ In the reaction the thiolate anion acts as the nucleophile while hydrogen peroxide and the transient sulfenic acid, RSOH, function as electrophiles.The most plausible mechanism for the copper-catalyzed, aerobic coupling reaction is as follows: Cu⁺ (RSSR)₂⁺ + RS⁻

(RSSR)Cu⁺ (RS⁻) + RSSR (RSSR)Cu⁺ (RS⁻) + RS⁻

(RSSR)Cu⁺ (RS⁻)₂⁻ (RSSR)Cu⁺ (RS⁻)₂⁻ + O₂

Cu⁺(RSSR)₂⁺ + HO₂⁻ rate-determining RS⁻ + H₂O₂

RSOH + OH⁻ rate-determining RS⁻ + RSOH → RSSR + OH⁻ For the n-propylthiol substrate, the pertinent parameters in the mechanism are 1n (K₁) = −11,000 K/T + 33.6, where K₁ is dimensionless, 1n (K₂) = 4270 K/T −10.5, where K₂ is in 1/mol, 1n (k₂) = 30.0 − 5260 K/T, and 1n (k₂) = 26.8 − 6190 K/T, where k₁ and k₂ are in 1/(mol min).     

Redox chemistry of highly dispersed rhodium in zeolite NaY

NaY zeolite exchanged with [Rh(NH₃)₅Cl]²⁺ ions have been studied using temperature programmed oxidation (TPO), temperature programmed reduction (TPR), and Fourier transformed infrared spectroscopy. The TPO profiles show that ammine ligands in NaY encaged [Rh(NH₃)₅Cl]²⁺ are destroyed above 300 °C, whereas the Rh precursor ion remains intact after calcination at 200 °C. TPR profiles in conjunction with the CO_ads IR spectra show that the reducibility of Rh by H₂ is largely controlled by the concentration of the surface protons, i.e. Rh³⁺+H₂Rh⁺+2H⁺ Rh⁺ + 1/2H₂Rh⁰+H⁺ In the presence of ammonia, the protons are neutralized and Rh³⁺ is reduced to Rh⁰. However, reduction remains incomplete when the concentration of protons is high. The ammonia was provided either by NH₃ admission or by conservation of ammine ligands by controlled calcination. CO adsorption does not lead to reoxidation of Rh⁰ particles to Rh⁺ ions.     

Active-oxygen species on non-reducible rare-earth-oxide-based catalysts in oxidative coupling of methane

From supplementary in situ Raman spectroscopic studies of active-oxygen species on non-reducible rare-earth-oxide-based catalysts in the oxidative coupling of methane (OCM) and structural adaptability considerations, further support has been obtained for our proposal that there may be an active and elusive precursor (of O₂ ^– and O₂ ^2– adspecies), most probably O₃ ^2– formed from reversible redox coupling of an O₂ adspecies at an anionic vacancy with a neighboring O^2– in the surface lattice. This active precursor may initiate H abstraction from CH₄ and be itself converted to OH^–+O₂ ^–, or it may abstract an electron from the oxide lattice and be converted to O₂ ^2–+O^–. The prospect of developing this type of OCM catalysts is discussed.     

Electrochemical properties of poly(decaviologen) in polymer media

Poly(decaviologen) (DV²⁺, 2ClO ₄ ^– ) has been prepared and used in the characterization of two redox couples; dication/cation radical ((DV²⁺, 2 ClO ₄ ^– )/(DV⁺, ClO ₄ ^– )) and cation radical/decaviologen ((DV⁺, ClO ₄ ^– )/(DV^o)) in a polyethylene oxide-LiClO₄ medium by linear potential sweep voltammetry. The (DC²⁺, 2 ClO ₄ ^– )/(DV⁺, ClO ₄ ^– ) couple has been used to determine the transport number of lithium in poly(ethylene oxide)–LiClO₄ or LiCF₃SO₃ complex media.     

Behavior of cesium cation in zeolite Y (FAU,Si/Al = 1.56) and their single-crystal structures, |Cs<Subscript>75−x</Subscript>Na<Subscript>x</Subscript>|[Si<Subscript>117</Subscript>Al<Subscript>75</Subscript>O<Subscript>384</Subscript>]-FAU (x = 35 and 54)

To study the tendency of Cs⁺ exchange into zeolite Y (Si/Al = 1.56) dependence on Cs⁺ and Na⁺ concentration of aqueous solution during exchange, two single-crystals of fully dehydrated, Cs⁺-and Na⁺-exchanged zeolites Y were prepared by the flow method using a mixed ion-exchange solution whose CsNO₃:NaNO₃ mol ratios were 1:1 (crystal 1) and 1:100 (crystal 2), respectively, with a total concentration of 0.1 M, followed by vacuum dehydration at 723 K. Their crystals were determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group Fd \(\overline{ 3}\) m, respectively, and were refined to the final error indices R ₁/wR ₂ = 0.084/0.248 and 0.088/0.274 for crystals 1 and 2, respectively. In the structure of |Cs₄₀Na₃₅|[Si₁₁₇Al₇₅O₃₈₄]-FAU (crystal 1), 40 Cs⁺ ions per unit cell occupy five different equipoints; 3, 3, 14, 9, and 11 are at sites I, II′, II, IIIa and IIIb, respectively, whereas, the remaining 35 Na⁺ ions occupy three different sites: 9, 11, and 15 are at sites I, I′, and II, respectively. In the structure of |Cs₂₁Na₅₄|[Si₁₁₇Al₇₅O₃₈₄]-FAU (crystal 2), 21 Cs ⁺ ions per unit cell occupy three equipoints; 4, 6, and 11 are at sites II, IIIa, and IIIb, respectively. The residual 54 Na⁺ ions per unit cell are found at three different sites; 6, 20 and 28 are at sites I, I′, and II, respectively. The degrees of ion exchange are 53 and 28 % for crystals 1and 2, respectively. This result shows that the degree of Cs⁺ exchange decreased sharply by decreasing the initial Cs⁺ concentration and increasing the initial Na⁺ concentration in given ion-exchange solution.     

New mononuclear CuII and ZnII complexes capable of stabilizing phenoxyl radicals as models for the active form of galactose oxidase

Herein, we describe the synthesis and crystal structure of mononuclear Cu^II and Zn^II complexes containing the new pentadentate H₂L ligand (H₂L = N-(methyl)-N^′-(2-pyridylmethyl)-N,N^′-bis(3,5-di-tert-butyl-2-hydroxybenzyl)-1,3-propanediamine. The [Cu^II(L)] and [Zn^II(L)] complexes and their one-electron oxidized [Cu^II]⁺ ([1]⁺) and [Zn^II]⁺ ([2]⁺) compounds exhibit electrochemical and spectroscopic (UV–Vis and EPR) features with relevant insight into the oxidizing half-reaction of the metalloenzyme galactose oxidase.     

Kinetic modeling and dynamic simulation for the catalytic wet air oxidation of aqueous ammonia to molecular nitrogen

A kinetic model for the catalytic wet air oxidation of aqueous ammonia over Ru/TiO₂ catalyst was developed considering the consecutive reaction steps as follows: (i) formation of active oxygen sites O* by the dissociative adsorption of aqueous O₂ on the catalyst, (ii) oxidation of aqueous NH₃ by the reaction with three O* sites to produce HNO₂, (iii) aqueous phase dissociation of HNO₂ into H⁺ and NO ₂ ^? , (iv) formation of NH ₄ ⁺ by the association of NH₃ with the HNO₂-dissociated H⁺, (v) formation of N₂ by the aqueous phase reaction between NO ₂ ^? and NH ₄ ⁺ , (vi) formation of NO₃ by the reaction of NO ₂ ^? with an O* site. For each reaction step, a rate equation was derived and its kinetic parameters were optimized by experimental data fitting. Activation energies for the reactions (ii), (v), and (vi) were 123.1, 76.7, and 54.5 kJ/mol, respectively, suggesting that the oxidation reaction of aqueous NH₃ to HNO₂ was a ratedetermining step. From the simulation using the kinetic parameters determined, the initial pH adjustment of the ammonia solution proved to be critical for determining the oxidation product selectivity between desirable N₂ and undesirable NO ₃ ^? as well as the degree of oxidation conversion of ammonia.     

Dissolution of nickel (74%)-copper (4%)-sulphide matte anode in acidic chloride solutions

A comparative study was conducted to assess the performance of 1 N solutions of hydrochloric acid, ferrous chloride and ferric chloride solutions to dissolve the 74% Ni-4% Cu-20% S nickel sulphide matte anodes. The essential variables considered here were: temperature (25° and 75° C), oxygen and controlled potential. The relative aggressiveness as estimated by the potentiokinetic polarization curves and dissolution experiments with open circuit can be arranged in the following sequence: Fe³⁺>Fe²⁺>H⁺. At +400 mV versus SCE, the aggressiveness reversed in the following sequence: H⁺>Fe²⁺>Fe³⁺. The experimental values of dissolution rates with open circuit and at constant potential were higher than those calculated from the dissolution current densities (potentiokinetic polarization curves), and from the amount of charge passed (at +400 mV versus SCE).Attack by intergranular dissolution and pitting was observed throughout these experiments. The formation of -NiS by the reaction Ni₃S₂ Ni²⁺+2-NiS+ 2e was confirmed by X-ray analysis. The above results are interpreted in the light of the possible electrochemical mechanisms.     

Selective catalytic reduction of NOx with methane over indium supported on tungstated zirconia

Selective catalytic reduction (SCR) of NO_x with methane was investigated over a series of non-noble metal (cobalt, manganese, nickel, tin, silver, indium) catalysts supported on tungstated zirconia (WZr). A great improvement of catalytic activity was found over the indium-loaded WZr catalysts upon the other WZr. The highest NO_x conversion of 70% was achieved over an 1%In/WZr catalyst at 450 °C and 12,000 h⁻¹. InO⁺ was proposed to be the active site in NO reduction. H₂O and SO₂ significantly inhibited NO reduction by competing with reactants to adsorb on InO⁺ site and forming inactive $\mathrm{In}(\mathrm{OH}{)}_2^{+}$ and In(SO₃)⁺ species.     

Electrochemical reduction of 2-nitroimidazole in aprotic medium: Influence of its dissociation equilibrium on the reduction mechanism

The electrochemical reduction of 2-nitroimidazole in a non-aqueous medium using cyclic voltammetry (CV) at a mercury electrode was carried out.The 2-nitroimidazole derivative in DMF + 0.1 M tetra(n-butyl)ammonium hexafluorophosphate (TBAHFP6) resulted in the following dissociation equilibrium:

HNRNO₂ ? ⁻NRNO₂ + H⁺     

Fe3+--gluconate and Ca2+-Fe3+--gluconate complexes as mediators for indirect cathodic reduction of vat dyes – Cyclic voltammetry and batch electrolysis experiments

The indirect cathodic reduction of dispersed vat dyes CI Vat Yellow 1 and CI Vat Blue 5 was investigated by cyclic voltammetry and with batch electrolysis experiments. 0.01molL^–1 solutions of the complexes Fe³⁺--gluconate and Ca²⁺-Fe³⁺--gluconate were studied. The addition of dispersed dyestuff to the mediator solution lead to a catalytic current. While the cathodic peak currents of both complexes is comparable, Fe³⁺-DGL shows higher enhancement factors, which are defined as quotient of catalytic peak current and cathodic peak current of the mediator system (I_p)_c/(I_p)_d. In the presence of 0.5gL^–1 of dispersed vat dye enhancement factors of 1.8 were determined at scan rates of 0.005–0.010Vs^–1. Galvanostatic batch reduction experiments with use of a laboratory multi-cathode cell confirmed the favourable properties of the Fe³⁺-DGL in comparison to the binuclear Ca²⁺-Fe³⁺-DGL. With use of the Fe³⁺-DGL mediator complete dyestuff reduction could be achieved. The batch reduction process was followed experimentally by photometry and redox potential measurement in the catholyte.     

Thermal and chemical ionization in flames

Conclusions We have determined the rate constants of the potassium ionization process AA⁺+e^– in the flames of 2H₂+O₂+X (Ar, He) mixtures on the temperature interval 1500–2500° K. The activation energy of this process is close to the ionization potential of potassium (100 kcal).In our experiments the rate of ion formation in the front of a hydrogen flame seeded with potassium exceeded the purely thermal ionization rate by 0.5–2 orders. The presumed cause is recombination ionization of the potassium in the flame front, for example, K+O+OK⁺+O₂+e^–. This is confirmed by the intensification of ionization in the reaction zone in the presence of an excess of oxygen in homogeneous H₂-air and H₂–O₂–(He, Ar) mixtures with alkali impurities.At T=1700° K the recombination coefficient for electrons and potassium ions is close to 1·10^–8 cm³·sec^–1. For a more precise determination it is necessary to know the frequency of electron capture by molecules and atoms under the experimental conditions.Experiments on thermal ionization in turbulent flames confirm the earlier conclusion concerning the important role of mass transfer in the chemi-ionization of hydrocarbon flames.Fizika Goreniya i Vzryva, Vol. 6, No. 1, pp. 37–48, 1970     

New host–guest supramolecular coordination polymers based on [(Me3Sn)3Fe(CN)6]n with alkali metal iodides and their applications as electrode materials in batteries

The metal iodides reduce partially the host coordination polymer of the type $ ^{ 3}_{\infty } \left[ {\left( {{\text{Me}}_{ 3} {\text{Sn}}} \right)_{ 3} {\text{Fe}}\left( {\text{CN}} \right)_{ 6} } \right] $ , I, to give new host–guest supramolecular coordination polymers (SCP). The physical and chemical characteristics of the new products were studied by elemental analyses, X-ray powder diffraction, IR, UV/Vis, and solid state NMR spectra. The host–guest SCP are [M_x(Me₃Sn)₃Fe_(1–x)^IIIFe _x ^II (CN)₆]_n M = Li⁺·2H₂O, 1; Li⁺, 2; Na⁺, 3; K⁺, 4; Cu⁺, 5, [Li(Me₃Sn)₃Fe^II(CN)₆]_n, 6 and [(LiDEE)_0.9(Me₃Sn)₃Fe _o.1 ^III Fe _o.9 ^II (CN)₆]_n, 7. The stoichiometry and nature of the guest depend on the type of the metal iodide and the reaction conditions. The polymeric nature of these SCP is due to the presence of trigonal bipyramidal configured structure which bridges between the single d-transition metal ions. The host–guest SCP containing the Li ions have been tested as electrodes to construct four different lithium-ion batteries.     

Kinetics of the metal exchange reaction of a Cu(II)-poly(vinyl alcohol) complex with Zn(II)-ethylenediamine-N,N,N′,N′-tetraacetic acid in aqueous solution

The kinetics of the metal exchange reaction between Cu(II)-poly(vinyl alcohol) [Cu(II)-PVA] and Zn(II)-ethylenediamine-N,N,N,N-tetraacetic acid [Zn(II)-EDTA] has been studied by mixing both solutions in a spectrophotometer at pH 10.0 to 11.0, ionic strength =0.10(KNO₃), and 15 to 35°C. The reaction is initiated by the formation of unstable Cu(II)-H-PVA through attack of H⁺ ion on the Cu(II)-PVA complex, and both reactions, ligand exchange and metal exchange, proceed simultaneously. The metal exchange step may be rate determining. The rate equation and rate constants of this reaction were determined as follows: –d[Cu(II)-PVA]/dt=k _0(H)[PVA^–][Cu(II)-PVA] [Zn(II)-EDTA], wherek _0(H)=k ₁+(k₂+k₃)[H⁺],k ₁=5.98±1.64M ^–1 s^–1, andk ₂+k ₃=k₂ K _Cu(II)-H-PVA ^–H +k₃ K _Zn(II)-EDTA ^H =(5.91±0.89)×10⁷ M ^–2 s^–1.