摘要
自Reiss等人于1960年前后创立了定标粒子液体理论以后,首先被Pierotti用来估算非极性气体在水中的溶解度,并将其逐渐发展成为我们今天的定标粒子溶液理论;1969年,Shoor-Gubbins应用Pierotti的上述理论模型来解决一系列非极性气体在不同浓度的KOH溶液中的溶解度问题,结果相当成功;此后,Masterton-Lee等人进一步发展这个理论并将其用来解决任意物质体系的溶解度和盐效应常数等问题,均得到了令人满意的结果。在我国,继黄子卿先生将定标粒子理论用于解决气体溶解度问题之后。
According to the theromodynamical formula of chemical equilibrium, for the reaction:we have: △G^0=-RT·In(Kα) or: △g^0=-k_bT·In(K_α) where, △g^0=g_(Ac)~0-+g_(H3O)~0+-g_(HAc)~0-g_(H2O)~0, g_j^0 is chemical potential or partial molecule Gibbs free-energy of solute j. According to the Scaled Particle Theory (SPT), the Gibbs free-energy of solute j in a solvent is consists of two parts,the first is called the cavitation free-energy (9_j^h), which is the energy needed to transfer a particle from the vacuum to the solvent, and, the second, the interaction free-energy, which contains four terms mainly: the induction energy (g_j^(IN)),the orientation energy(g_j^(OR)), the dispersion energy (g_j^(DS)) and the static energy (g_j^(EL)), So: then we have: K_α/k_α~0=exp(-△g^0/k_bT) where K_α is the ionization constant of HAc in the vacuum, and,is unknown.To solve the problom, we have to select another standard solvent in which, the K_α'of HAc is well known.of course, water is the best one,in it,the K_α' of HAc is 1.754×10^(-5) at 298 K, and finally we have where: △(△g^0)=△g^0(in the solvent studying)-△9~0' (in water)According to the theory and formula developed above,we took a series of MeOH-Water mixtures and 1,4-Dioxane-Water mixtures as example in this article, and calculated the K_α of HAc in those mixtures.By comparing the values with that from literatures we found that they are accordance well when the weight per-cent of the non-water conponents is less than 90% and not as larger than 90%.The reasons causing the results are discussed mainly at the end.
出处
《物理化学学报》
SCIE
CAS
CSCD
北大核心
1989年第6期739-744,共6页
Acta Physico-Chimica Sinica
