CIESC Journal

• 化工学报 •    下一篇

氧化铜与二氧化硫及氧作用生成硫酸铜的动力学

陈家镛,夏光祥   

  1. 中国科学院化工冶金研究所 ,中国科学院化工冶金研究所
  • 出版日期:1965-03-25 发布日期:1965-03-25

THE KINETICS OF CuO REACTING WITH GASEOUS SO_2 AND O_2

CHEN CHIA-YUNG AND HSIA KWANG-HSIANG (Institute of Chemical Metallurgy,Academia Sinica)   

  • Online:1965-03-25 Published:1965-03-25

摘要: 在不同温度及气相组成下,曾对氧化铜与SO_2及O_2作用生成硫酸铜的动力学进行了研究。 反应先生成盐基性硫酸铜,然后再生成硫酸铜。俟硫酸铜生成量达30%后,形成一硬壳,此时反应为气体通过硬壳层的扩散所控制。 当反应仅生成盐基性硫酸铜时,盐基性硫酸铜生成的百分数f_b=a+b_t;t为时间,a及b为常数。生成硫酸铜时,硫酸铜的最初生成百分数f_c=kt。俟硬壳形成后,反应即减慢。 在硬壳未形成之前,生成盐基性硫酸铜及硫酸铜的速度均可用下式表示: R_(av)=(k_1·PSO_2)/(1+k_2·(PO_2)~(1/2)+k_3·PSO_2) 式中R_(av)为时间平均反应速度,PSO_2及PO_2分别为SO_2及O_2的分压,k_1、k_2及k_3为常数。实验结果推论出反应为表面上氧离子上吸附的SO_2进一步作用为SO_4~(-2)的速度所控制。当气相中没有氧存在时,反应结果尚生成氧化亚铜。由于氧化亚铜系p-型半导体,因此反应较有氧气存在时为快。当气相中有SO_3存在时,反应速度较仅有SO_2及O_2存在时为快。在此种情况下,反应机理估计与目前结论完全不同。

Abstract: Studies were made on the kinetics of CuO reacting with gaseous mixtures of SO2, O2 and N2 of different compositions at temperatures ranging from 200 to 700℃. At low temperatures the reaction product is basic copper sulfate. Copper Sulfate is found at high temperatures and only after a large amount of basic sulfate has been formed. After about 30% of the original CuO has been converted into copper sulfate, a hard non-permeable copper sulfate layer is produced around the sample. Further reaction is controlled by gaseous diffusion through this reaction product layer. The amount of basic sulfate and normal sulfate produced has been found to increase linearly with reaction time before the formation of the non-permeable layer. The rate of formation of basic sulfate in the low temperature range and normal sulfate in the high temperature range can be represented by the following equation. where Rav. is the time-average reaction rate in weight percent per unit time; psO2 and pO2 are the partial pressures of S02 and O2 respectively;k1 k2 and k3 are constants. A reaction mechanism has been postulated. The reaction rate is considered to be controlled by the formation of sulfate ion on the solid surface between the adsorbed SO2 on the oxygen ion and another oxygen ion. In the absence of O2 in the gas phase, Cu3O is also formed as a reaction product. As Cu2O is a p-type semiconductor, the reaction rate is increased under this condition. The reaction follows a different mechanism with SO3 in the gaseous mixture, to which the present conclusion does not apply.