The Use of Adiabatic Calorimetry for the Process Analysis and Safety Evaluation in Free Radical Polymerization

Adiabatic calorimetry is a technique that has been introduced as an important approach to hazard evaluation of exothermically reactive systems. In this paper the free radical polymerization of methyl methacrylate (MMA) has been studied. One of the most important aspects of MMA polymerization is its exothermicity and autoaccelerating behaviour, these characteristics can generate the occurrence of a runaway reaction.In a runaway situation the reacting system is close to adiabatic behaviour because it is unable to eliminate the heat that is being generated. An even worse situation can be reproduced in the laboratory with the Phi-Tec pseudo-adiabatic calorimeter. Process design parameters that are usually calculated from thermodynamic data or using semiempirical rules, such as adiabatic temperature rise or maximum attainable pressure, can be directly determined.The existence of the ceiling temperature has been experimentally demonstrated.This revised version was published online in November 2005 with corrections to the Cover Date.     

Spins of198Au levels from the (n, γ) reaction using polarized neutrons and polarized197Au nuclei

The¹⁹⁷Au(n, γ) reaction was studied with the aid of polarized thermal neutron beams. Two kinds of experimental data were obtained: i) circular polarization of gamma rays of high energy due to capture of polarized neutrons by unoriented¹⁹⁷Au nuclei, and ii) angular distribution of such gamma rays observed after capture of polarized neutrons by polarized¹⁹⁷Au nuclei. Spins of several levels of¹⁹⁸Au could be uniquely assigned or could be restricted. The sign of the hyperfine field of Au in AuFe has been determined to be negative.     

分散在(Ga1-xZnx)(N1-xOx)载体上的Rh纳米颗粒尺寸对光催化氧化反应的作用（英文）

Mixed Ga–Zn oxynitrides were synthesized using coprecipitation, wet-precipitation, and sol-id-solution methods. The oxynitrides were used as supports for Rh nanoparticle catalysts in photo-catalytic water splitting, CO oxidation, and H2 oxidation. Mixed Ga–Zn oxynitrides produced by wet precipitation and nitridation had good visible-light-absorption properties and high surface areas, so they were used to support uniformly sized poly(vinylpyrrolidone)-stabilized Rh nanoparticles. The nanoparticle size range was 2–9 nm. These catalysts had negligible activity in photocatalytic H2 production by water splitting with methanol as a sacrificial agent. Other mixed Ga–Zn oxynitrides were also inactive. A reference sample provided by Domen also showed very low activity. The in-fluence of particle size on Rh-catalyzed oxidation of CO and H2 was investigated. For CO oxidation, the activities of small particles were higher for particles with higher Rh oxidation degrees. The op-posite holds for H2 oxidation.     

Pd-catalyzed amidation of 2-chloro- and 2,7-dichloro-1,8-naphthyridines

[reactions: see text] The catalytic amidation between 2-chloro- and 2,7-dichloro-1,8-naphthyridines and primary amides bearing functional groups is reported. When Pd(OAc)2, xantphos, and K2CO3 are used, it is possible to obtain symmetric as well as nonsymmetric 2,7-diamido-1,8-naphthyridines in 50-90% yield with good functional-group tolerance. Monoamidation of 2,7-dichloro-1,8-naphthyridine using 0.9 equiv of the amide proceeded with good selectivity compared to the formation of the diamide, but as a result of the difficult isolation of the product, isolated yields were poor to moderate (22-42%).     

Complementary quadruple hydrogen bonding in supramolecular copolymers

This paper describes a supramolecular copolymer based on quadruple hydrogen bonding between self-complementary ureido-pyrimidinones and complementary 2,7-diamido-1,8-naphthyridines. In contrast to previously reported polymer systems solely based on complementary hydrogen-bonding units, these polymers retain a high DP over a broad composition range.     

分散在(Ga_(1-x)Zn_x)(N_(1-x)O_x)载体上的Rh纳米颗粒尺寸对光催化氧化反应的作用(英文)

Mixed Ga–Zn oxynitrides were synthesized using coprecipitation, wet-precipitation, and sol-id-solution methods. The oxynitrides were used as supports for Rh nanoparticle catalysts in photo-catalytic water splitting, CO oxidation, and H2 oxidation. Mixed Ga–Zn oxynitrides produced by wet precipitation and nitridation had good visible-light-absorption properties and high surface areas, so they were used to support uniformly sized poly(vinylpyrrolidone)-stabilized Rh nanoparticles. The nanoparticle size range was 2–9 nm. These catalysts had negligible activity in photocatalytic H2 production by water splitting with methanol as a sacrificial agent. Other mixed Ga–Zn oxynitrides were also inactive. A reference sample provided by Domen also showed very low activity. The in-fluence of particle size on Rh-catalyzed oxidation of CO and H2 was investigated. For CO oxidation, the activities of small particles were higher for particles with higher Rh oxidation degrees. The op-posite holds for H2 oxidation.     

The mechanism of ureido-pyrimidinone:2,7-diamido-naphthyridine complexation and the presence of kinetically controlled pathways in multicomponent hydrogen-bonded systems

The kinetics of association of ureido-pyrimidinone (U) dimers, present either in the 4[1H]-keto form or in the pyrimidin-4-ol form, with 2,7-diamido-1,8-naphthyridine (N) into a complementary heterodimer have been investigated. The formation of heterodimers with 2,7-diamido-1,8-naphthyridine from pyrimidin-4-ol dimers is much faster than from 4[1H]-pyrimidinone dimers. Using a combination of simple measurements and simulations, evidence for a bimolecular tautomerization step is presented. Finally, the acquired kinetic knowledge of the different pathways leading from ureido-pyrimidinone homodimers to ureido-pyrimidinone:diamido-naphthyridine (U:N) heterodimers allows the prediction and observation of kinetically determined ureido-pyrimidinone heterodimers which slowly convert back to the corresponding homodimers.