CIESC Journal

• 化工学报 • 上一篇    下一篇

元素硫的歧化反应动力学研究

邓彤,柯家骏,陈家镛   

  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 ,中国科学院化工冶金研究所
  • 出版日期:1984-12-25 发布日期:1984-12-25

Kinetics of Disproportionation of Elemental Sulfur in Aqueous Solutions

Deng Tong, Ke Jiajun and Chen Jiayong Institute of Chemical Metallurgy, Academia Sinica   

  • Online:1984-12-25 Published:1984-12-25

摘要: 本文研究了在pH 6—10、温度130—170℃条件下元素硫在水溶液中的歧化反应,确定了反应式为4S+6OH~-→2S~(2-)+S_2O_3~(2-)+3H_2O.参考了伴有化学反应的相间传质模型,本文中导出伴有快速化学反应的相间传质模型,即-In(1-a)=k_tt.在pH6—7.5范围内进行动力学测定所得结果与该模型相符,且发现此歧化的化学反应速度与〔OH~-〕成正比,求得表观反应活化能为24.0千卡/克分子.同时,还研究了Cu~(2+)对元素硫在水溶液中歧化反应的影响.

Abstract: The hydrothermal sulfidization process, which has attracted attention in recent years, involves the disproportionation of elemental sulfur in aqueous solution. The kinetics of this disproportionation reaction was carried out. The effect of cupric ions in aqueous solution on this reaction was also investigated. The reaction was carried out in an autoclave. It was shown that elemental sulfur disproportionated in aqueous solutions of pH 6-10 according to the following equation: Experimental results can be correlated by a model of diffusion of elemental sulfur from sulfur droplets to the aqueous solution followed by a pseudo-first-order disproportionation reaction in the aqueous phase. The rate expression has the following form: -ln(1-α)=kt·t where kt = aCs, a is the interfacial area of 1 g of liquid sulfur in water, k1 is the pseudo-first-order reaction rate constant, Cs and D1 are solubility and diffusion coefficient respectively of sulfur in the aqueous phase, α is the fraction of conversion of elemental sulfur, and t is the time of reaction. The effect of pH on reaction rate was studied at 130℃. It was shown that the pseudo-first-order rate constant k1 is directly proportional to the concentration of OH- in the pH range of 6-7.5. The temperature dependence of k, was also studied at pH 6.3 and the apparent activation energy derived was 24.0 kcal/mol.