化学学报 ›› 1966, Vol. 32 ›› Issue (1): 1-6.    下一篇

论文

正庚烷的气相低温缓慢氧化

陈尚贤, 徐友乾, 吕锡恩, 胡日恒   

  1. 中国科学院化学研究所
  • 投稿日期:1964-05-06 发布日期:2013-06-03

SLOW OXIDATION OF n-HEPTANE IN GAS PHASE

CHEN Shang-Xian, XU You-Qian, LÜ Xi-En, HU Jih-Heng   

  1. Institute of Chemistry, Academia Sinica
  • Received:1964-05-06 Published:2013-06-03

本文研究在230℃静态系统中正庚烷的缓慢氧化,测定不同成分的压力-时间曲线(△p-t曲线),以及一个成分下的产物(总醛量、过氧化氢、有机过氧化物、酸)随时间变化的关系(成分-时间曲线).利用汞能够破坏过氧化物,将部分氧化的反应混合物抽出反应瓶,部分地破坏过氧化物后再放入反应瓶中,从而研究过氧化物对产物的影响.这些研究的结果表明,除非氧压力小于50毫米汞柱,否则氧压力对反应速度影响很少,而反应速度是随正庚烷的压力的增加而增加,过氧化物对反应的影响非常大,因而可能是本文实验条件下的退化分支物质.反应产物对反应也有阻化作用,但何种物质起阻化作用尚未找出.

The slow oxidation of n-heptane was studied at 230° in a static system.The influence of heptane and oxygen pressures on the reaction sates was examined.The results show that maximum reaction rates increases with the pressure of heptane but do not depend on the pressure of oxygen,unless the latter is less than 50 mm Hg.Two different types of p-t curves have been found: The first type which occurs when pRH:pO2>0.2,is characterized by no change of pressure at the beginning of the reaction.The second type which occurs when pRH: pO2<0.2,starts with a pressure drop.The amount of total aldehydes,hydrogen peroxides,total organic peroxides,and total organic acids in the system were determined analytically at various times.The particular influence of peroxides on the reaction was examined by pumping the reaction mixture into a mercury reservoir to partially destroy the peroxides,and then introducing the reaction mixtures back to the reaction vessel.A great decrease of reaction rate was observed,indicating that the peroxides function as degenerate-branching agent.It was observed that the reaction was inhibited by its reaction products.