Recently, the existence of a relation between the rupture of 1,4-β-glycosidic bonds in the cellulose during thermal-ageing of paper/oil systems and the detection of methanol in the oil has been reported for the first time in this journal (Jalbert et al. 2007). The present study addresses the rate constants of the reaction for standard wood kraft papers, two immersed in inhibited naphthenic oil under air (paper/oil weight–volume ratio of 1:18) and one in non-inhibited paraffinic oil under nitrogen (paper/oil weight–volume ratio of 1:30). The isotherms in the range of 60–130 °C show that the initial rate of methanol production markedly increases with temperature and to a lesser extent with the moisture of the specimens (initially between 0.5 and 2.25% (w/w)), similarly to what is noted for the depolymerization through the Ekenstam’s pseudo-zero order model. The Arrhenius expression of the rate constants reveals linear relationships that confirm the dominance of a given mechanism in both cases. A very good agreement is also noted for the activation energy over the entirely paper/oil systems studied (106.9 ± 4.3 and 103.5 ± 3.7 kJ mol?1 for methanol and scissions, respectively). Furthermore, a comparison of the rate constants $ \left( {k_{{{\text{CH}}_{ 3} {\text{OH}}}} /k_{\text{scissions}} } \right) Recently, the existence of a relation between the rupture of 1,4-β-glycosidic bonds in the cellulose during thermal-ageing of paper/oil systems and the detection of methanol in the oil has
been reported for the first time in this journal (Jalbert et al. 2007). The present study addresses the rate constants of the reaction for standard wood kraft papers, two immersed in inhibited
naphthenic oil under air (paper/oil weight–volume ratio of 1:18) and one in non-inhibited paraffinic oil under nitrogen (paper/oil
weight–volume ratio of 1:30). The isotherms in the range of 60–130 °C show that the initial rate of methanol production markedly
increases with temperature and to a lesser extent with the moisture of the specimens (initially between 0.5 and 2.25% (w/w)),
similarly to what is noted for the depolymerization through the Ekenstam’s pseudo-zero order model. The Arrhenius expression
of the rate constants reveals linear relationships that confirm the dominance of a given mechanism in both cases. A very good
agreement is also noted for the activation energy over the entirely paper/oil systems studied (106.9 ± 4.3 and 103.5 ± 3.7 kJ mol−1 for methanol and scissions, respectively). Furthermore, a comparison of the rate constants shows approximately constant values indicating an apparent yield for the methanol of about one-third molecule per every scission
for the tests under air (0.27 ± 0.04 for Clupak HD75 and 0.37 ± 0.14 for Munksj? TH70) and even lower for the ones under N2 (0.12 ± 0.03 for Munksj? E.G.). As expected from a pseudo-zero order model, these values were shown to be consistent with
a similar comparison of the amount of CH3OH and chain-end groups produced under specific time–temperature ageing conditions (168 h at 120 °C). Finally, an additional
test carried out with unaged cellulose in contact with a fresh solution of methanol in oil (cellulose/oil weight–volume ratio
of 1:18) shows that at equilibrium, over 58% of the species is lost from the solution due to penetration into the fibres.
Such results reveal the importance of the species partitioning in establishing the true correspondence between the molecules
of CH3OH produced and the scissions. 相似文献
From urea to nucleobases : Freeze–thaw cycles in urea ( 1 ) solutions under methane/nitrogen atmospheres lead, with application of an energy source, to the synthesis of pyrimidines (mainly cytosine ( 2 ) and uracil ( 3 )), triazines (such as cyanuric acid ( 4 )), and adenine. This synthesis appears to be dependent on the atmosphere and the freezing conditions. At room temperature, hydantoin ( 5 ) is obtained. However, a freezing urea/water system subjected to an energy source under an inert atmosphere generates s‐triazines.
Recently, there has been great interest in developing advanced sodium‐ion batteries for large‐scale application. Most efforts have concentrated on the search for high‐performance electrode materials only in sodium half‐cells. Research on sodium full cells for practical application has encountered many problems, such as insufficient cycles with rapid capacity decay, low safety, and low operating voltage. Herein, we present a layered P2‐Na0.66Ni0.17Co0.17Ti0.66O2, as both an anode (ca. 0.69 V versus Na+/Na) and as a high‐voltage cathode (ca. 3.74 V versus Na+/Na). The full cell based on this bipolar electrode exhibits well‐defined voltage plateaus near 3.10 V, which is the highest average voltage in the symmetric cells. It also shows the longest cycle life (75.9 % capacity retention after 1000 cycles) in all sodium full cells, a usable capacity of 92 mAh g?1, and superior rate capability (65 mAh g?1 at a high rate of 2C). 相似文献
The formation of peptides and then protein by small abiological molecules clusters such as amino acid is a key stage in the origin of life[1]. More and more ex- perimental results showed that phosphate plays an important role in the formation of biomolecules in prebiotic chemical evolution. The principal reservoirs of biochemical energy are phosphates (such as ATP). The peculiar role of phosphates in contemporary life might suggest its essential role in prebiotic energy conversion, syntheses … 相似文献
