Hirokawa Jun, Kato Takehiro, Mafuné Fumitaka
Faculty of Environmental Earth Science, Hokkaido University, Kita-10, Nishi-5, Sapporo, 060-0810, Japan.
J Phys Chem A. 2008 Nov 27;112(47):12143-50. doi: 10.1021/jp8051483.
Uptake kinetics of gas phase nitrous acid (HONO) by a pH-controlled aqueous solution was investigated by using a wetted wall flow tube. The gas phase concentration of HONO after exposure to the aqueous solution was measured selectively by the chemical ionization mass spectrometer in a high sensitive manner. The uptake rate of the gaseous HONO was found to depend on the pH of the solution. For the uptake by neutral and alkaline solutions, the gas phase concentration was observed to decay exponentially, suggesting that the uptake was fully limited by the gas phase diffusion. On the other hand, the uptake by the acidic solution was found to be determined by both the gas phase diffusion and the liquid phase processes such as physical absorption and reversible acid dissociation reaction. The decay was analyzed by the rate equations using the time dependent uptake coefficient involving the saturation of the liquid surface. While the uptake processes by the solution at pH = 2-3 were well described by those calculated using the physical and chemical parameters reported for the bulk, the uptake rates by the solution at 4 < pH < 7 deviate from the calculated ones. The present result can suggest that the pH at the liquid surface is lower than that in the bulk liquid, which is responsible for the additional resistance of mass transfer from the gas to the liquid phase.
采用湿壁流管研究了pH值控制的水溶液对气相亚硝酸(HONO)的吸收动力学。通过化学电离质谱仪以高灵敏度选择性地测量暴露于水溶液后气相中HONO的浓度。发现气态HONO的吸收速率取决于溶液的pH值。对于中性和碱性溶液的吸收,观察到气相浓度呈指数衰减,这表明吸收完全受气相扩散限制。另一方面,发现酸性溶液的吸收由气相扩散和诸如物理吸收及可逆酸解离反应等液相过程共同决定。利用包含液体表面饱和的时间相关吸收系数的速率方程对衰减进行了分析。虽然pH = 2 - 3的溶液的吸收过程可以很好地用根据本体报道的物理和化学参数计算得到的结果来描述,但pH在4 < pH < 7的溶液的吸收速率与计算值存在偏差。目前的结果表明,液体表面的pH值低于本体液体中的pH值,这是造成从气相到液相传质额外阻力的原因。