A study of the solid-phase thermal decomposition of NTO using simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS)

The solid phase thermal reaction chemistry of NTO between 190 and 250 C is presently being evaluated by utilizing STMBMS, a technique that enables the authors to measure the vapor pressure of NTO and to explore the reaction mechanisms and chemical kinetics associated with the NTO thermal decomposition process. The vapor pressure of NTO is expressed as Log{sub 10} p(torr) = 12.5137 + 6,296.553(1/t{sub k}) and the {Delta}H{sub subl} = 28.71 {+-} 0.07 kcal/mol (120.01 {+-} 0.29 kJ/mol). The pyrolysis of NTO results in the formation of gaseous products and a condensed-phase residue. The identity of the major gaseous products and their origin from within the NTO molecules are determined based on the results from pyrolysis of NTO, NTO-3-{sup 13}C, NTO-1,2-{sup 15}N{sub 2} and NTO-{sup 2}H{sub 2}. Identification of the products show the major gaseous products to be N{sub 2}, CO{sub 2}, NO, HNCO, H{sub 2}O and some N{sub 2}O, CO, HCN and NH{sub 3}. The N{sub 2} is mostly derived from the N-1 and N-2 positions with some being from the N-4 and N-1 or N-2 positions. The CO{sub 2} is derived from both carbons in the NTO molecule in comparable amounts. The residue has an elemental formula of C{sub 2.1}H{sub .26}N{sub 2.9}O and FTIR analysis suggests that the residue is polyurea- and polycarbamate-like in nature. The temporal behaviors of the rates of formation of the gaseous products indicate that the overall thermal decomposition of NTO in the temperature range evaluated involves four major processes: (1) NTO sublimation; (2) an apparent solid-solid phase transition between 190 and 195 C; (3) a decomposition regime induced by the presence of exogenous H{sub 2}O at the onset of decomposition; and (4) a decomposition regime that occurs at the onset of decomposition and continues until the depletion of NTO. Decomposition pathways that are consistent with the data are presented

Chemically induced dynamic electron polarization of the diethoxyphosphonyl radical: A case of mixed S-T0 and S-T- radical pair polarization

The electron spin resonance spectrum of the diethoxyphosphonyl radical, (EtO)2\u1e56O, which is characterized by a well-spaced 696-G doublet, exhibits a strong electron polarization when generated by photolysis of a 20% (v/v) solution of diethyl phosphite in di-tert-butyl peroxide. Although the observed emissive-absorptive polarization superficially appears due to the usual S-T0 radical pair mechanism, a detailed analysis shows that the S-T_ radical pair mechanism also contributes to the polarization. The analysis also yields an estimate of the range of the exchange interaction between two (EtO)2\u1e56O radicals. \ua9 1985 American Chemical Society.Peer reviewed: YesNRC publication: Ye

Predação de ninhos artificiais em uma ilha na Mata Atlântica: testando o local e o tipo de ovo Artificial nest predation in Atlantic Forest Island: testing the place and the different types of egg

Experimentos com ninhos artificiais são utilizados para testar hipóteses ecológicas e comportamentais que influenciam na predação de ninhos naturais. O tamanho do ovo, a textura da casca e a cor podem influenciar na taxa de predação, porém poucos estudos avaliam qual modelo de ovo é o mais adequado para simular a predação de ninhos em áreas tropicais. O objetivo deste trabalho foi comparar a predação de diferentes modelos de ovos (ovos de codorna, massa de modelar e canários) no solo e a 1,30 m de altura no sub-bosque. O experimento foi realizado Ilha Anchieta, Ubatuba, São Paulo, Brasil. Foi encontrada uma diferença significativa na taxa de predação entre os ovos de codorna (71,87%) e sintéticos (93,75%) e entre os ovos de codorna e de canário (100%) no solo. Entretanto, não houve diferença significativa entre os ovos sintéticos e de canário. Os ninhos no sub-bosque apresentaram um padrão diferenciado do solo quando se refere aos ovos de codorna (25%) e sintéticos (28,1%), mas houve diferenças significativas quando os ovos de canário foram comparados com os ovos sintéticos e de codorna. Nosso trabalho demonstrou que diferentes tipos de ovos sobre uma mesma pressão de mesopredadores apresentaram taxas de predação diferentes. Portanto, estudos que avaliam o sucesso reprodutivo da avifauna baseado na predação de ninhos artificiais devem considerar a utilização de diferentes tipos de ovos e estratos na vegetação.<br>Experiments on artificial nests are usually used to test ecological hypothesis and behavioural that affects the predation of natural bird nests. It is has been discussed about the size of the egg, texture and color affecting predation rate, but a few studies evaluate which egg type is more appropriate to simulate nest predation in tropical areas. The objective of this work was to compare the predation of different models of eggs (Coturnix coturnix, plasticine and Serinus canarius) on the ground and understory in a island with high abundance of nest predators. The study was carry out in October 2004 at Anchieta Island, Ubatuba, São Paulo, Brazil. The nests on the ground showed a statistical significance difference in the predation of quail eggs, plasticine and canary eggs. However, we did not find differences between plasticine and canaries eggs. The nests in the understory had a different pattern on the ground of quail eggs (25%) and plasticine (28%) and there was a difference when we compare canary eggs with plasticine and quail eggs. Our work pointed out that different eggs may have different predation rates. Therefore, studies that evaluate reproductive fitness of the bird community based on artificial nests must considered different egg types and strata