Critical behavior of the aqueous electrolytic system 3-methylpyridine+D2O+NaBr

The system 3-methylpyridine(3MP) + water(H2O)+NaBr has been the subject of an intense scientific debate since the work of Jacob et al. [Phys. Rev. E. 58, 2188 (1988)] and Anisimov et al. [Phys. Rev. Lett. 85, 2336 (2000)]. The crossover critical behavior of this system seemed to show remarkable sensitivity to the weight fraction (X) of the ionic impurity NaBr. In the range X< or =0.10 the system displayed Ising behavior and a pronounced crossover to mean-field behavior in the range 0.10< or =X< or =0.16. A complete mean-field behavior was observed at X=0.17, a result that was later attributed to the existence of long-living nonequilibrium states in this system [Kostko et al., Phys. Rev. E. 70, 026118 (2004)]. In this paper, we report the near-critical behavior of osmotic susceptibility in the isotopically related ternary system, 3MP+heavy water(D2O)+NaBr. Detailed light-scattering experiments performed at exactly the same NaBr concentrations as investigated by Jacob et al. reveal that the system 3MP + D2O + NaBr shows a simple Ising-type critical behavior with gamma approximately 1.24 and nu approximately 0.63 over the entire NaBr concentration range 0< or =X< or =0.1900. The crossover behavior is predominantly nonmonotonic and is completed well outside the critical domain. An analysis in terms of the effective susceptibility exponent (gammaeff) reveals that the crossover behavior is nonmonotonic for 0< or =X< or =0.1793 and tends to become monotonic for X>0.1793. The correlation length amplitude xio, has a value of approximately 2 A for 0.0250< or =X< or =0.1900, whereas for X=0, xio approximately 3.179 A. Since isotopic H-->D substitution is not expected to change the critical behavior of the system, our results support the recent results obtained by Kostko et al. [Phys. Rev. E. 70, 026118 (2004)] that 3MP + H2O + NaBr exhibits universal Ising-type critical behavior typical for other aqueous solutions.     

Conversion of methanol into hydrocarbons over zeolite H-ZSM-5: ethene formation is mechanistically separated from the formation of higher alkenes

The widely debated reaction mechanism for the conversion of methanol to hydrocarbons over acidic zeolite H-ZSM-5 has been investigated using isotopic labeling. The mechanistic findings for H-ZSM-5 are clearly different from those previously described at a detailed level for H-beta and H-SAPO-34 catalysts. On the basis of the current set of data, we can state that, for H-ZSM-5, ethene appears to be formed exclusively from the xylenes and trimethylbenzenes. Moreover, propene and higher alkenes are to a significant extent formed from alkene methylations and interconversions. This implies that ethene formation is mechanistically separated from the formation of higher alkenes, an insight of utmost importance for understanding and possibly controlling the ethene/propene selectivity in methanol-to-alkenes catalysis.     

Solution to an open problem: a characterization of conditionally cancellative t-subnorms

In this work we solve an open problem of U. H?hle (Klement et?al. Fuzzy Sets Syst 145:471–479, 2004, Problem 11). We show that the solution gives a characterization of all conditionally cancellative t-subnorms. Further, we give an equivalence condition under which a conditionally cancellative t-subnorm has 1 as its neutral element and hence show that conditionally cancellative t-subnorms whose natural negations are strong are, in fact, t-norms.     

Design and fabrication of an ultraviolet photoelectron spectrometer for the study of free molecules

An ultraviolet photoelectron spectrometer for the study of free atoms and molecules has been designed and fabricated with indigeneous components. The spectrometer consists of a 100 mA HeI discharge lamp, 180° hemispherical electron energy analyser (127 mm mean dia) and electron multiplier ratemeter electron detection systems. The resolution of the spectrometer is 90 meV/and the intensity of N₂ (5σ) band is 10⁵ c/sec. The sample inlet and the collision chamber can be heated to 500 K so that solids of low vapour pressure can be studied. Typical spectra of molecules recorded with the instrument are shown. Contribution No. 373 from the Solid State and Structural Chemistry Unit.     

s-Prime elements in multiplicative lattices

Let be aC-lattice which is strong join principally generated. In this paper, we consider prime elements of for which every semiprimary element is primary. We show, for example, that a compact nonmaximal primep with this property is principal. We also show that if every primepm has this property, then is either a one dimensional domain or a primary lattice. It follows that if every primep satisfies the property, and if there are only a finite number of minimal primes in , then is the finite direct product of one-dimensional domains and primary lattices.     

Kinetics and mechanism of chlorination of p-aminobenzoic acid by chloramine-B

The chlorination of p-aminobenzoic acid (PABA) by chloramine-B (CAB) in HCl medium at 303 K indicates simultaneous catalysis by H⁺ and Cl^–. The reaction is first order in [CAB] and [HCl], but fractional order in [PABA]. The observed solvent isotope effect is 1.52. A suitable mechanism is proposed.

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- (PABA) -B (CAB) HCl 303 H⁺ Cl^–. [PABA]. 1,52. .

     

Synthesis,characterization and charge-transfer photochemistry of trans-aquo azido-N,N′-trimethylenebis(naphthylideneiminato)chromium(III)

A new Cr^III complex, viz. trans-[Cr(naphprn)(H₂O)₂]ClO₄·2H₂O, (1) {naphprn=N,N-trimethylenebis(naphthylideneimine)} has been synthesized and characterized. Aquo ligand substitution of ( 1 ) by the azide ligand gave rise to trans-[Cr(naphprn)(N₃)(H₂O)], ( 2 ). Irradiation of ( 2) in DMF gave nitrido(naphprn)chromium(V) ( 3 ). Solutions of ( 3 ) showed e.p.r. spectra at room temperature (g _iso=1.9865). The i.r. spectra showed disappearance of a band at 2067cm^–1 showing the breakdown of NN and appearance of a new band at 1074cm^–1which is assigned to the Cr¹⁴N, stretching frequency indicating the formation of a nitrido chromium(V) complex, ( 3). The u.v.–vis. spectrum of complex ( 3 ) exhibited a d–d band maximum at 553nm (=120M^–1cm^–1). The rate of formation of ( 2 ) was found to be 5.0×10^–3M^–1s^–1 in an aqueous acidic medium at [Cr^III]=0.5×10^–3M; [N₃ ^–]=0.01–0.15M; [H⁺]=0.001M and I=0.2M (LiClO₄). The rate of photo-decomposition of ( 2 ) to give rise to ( 3 ) was found to be 0.15×10^–3s^–1 in DMF.     

Selective reduction of alkenes, α,β-unsaturated carbonyl compounds, nitroarenes, nitroso compounds, N,N-hydrogenolysis of azo and hydrazo functions as well as simultaneous hydrodehalogenation and reduction of substituted aryl halides over PdMCM-41 catalyst under transfer hydrogen conditions

Chemoselective reductions of alkenes, α,β-unsaturated carbonyl compounds, nitro and nitroso compounds, N,N-hydrogenolysis of azo and hydrazo functions as well as simultaneous reduction and hydrodehalogenation of substituted aryl halides, including bulkier substrates, were achieved by catalytic transfer hydrogenation (CTH) using mesoporous PdMCM-41 catalyst. The yields were practically unaffected upon recycling of the catalyst. Further, the CTH process is accomplished without affecting the reduction of any other reducible functional group.     

LIGHT-INDUCED CAROTENE SYNTHESIS IN MUTANTS OF PHYCOMYCES WITH ABNORMAL PHOTOTROPISM

Mutants of Phycomyces. abnormal in their phototropic responses (the mad mutants), have been tested for their responses in light-induced carotene synthesis (LICS). The amount of carotene synthesized at any given fluence is significantly lower in the madA, madB and madD mutants than in the wild type. The amount of carotene is not lower in other mad mutants ( madC, madE, madF and madG ). The double mutant mad A madB and the triple mutant mad A madB madC show stronger effects. The wild type strain, as well as those carrying a single mad mutation ( madA and madB ) or those carrying two or three mad mutations ( madA madB. madA madB madC ) show closely similar sensitivity to LICS. This contrasts with phototropism and photoinitiation of sporangiophores which are sensitive to extremely small signals in the wild type and in which the madA mutation decreases the sensitivity by nearly a factor of 10⁴ and madB mutation by a factor of 10⁵. It appears that LICS does not share the signal amplification mechanisms characteristic of the other two responses.