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本文利用无水皂化萃取剂加水生成微乳状液研究离子水化的新方法,研究了酸性膦酸酯D_2EHPA(碱金属盐)-ROH-煤油-水体系中,通过对水质子化学位移变化的规律来研究碱金属的水合作用,所得结果与环烷酸体系相似。当[M~+]/[H_2O]从100/1向1/100变化时,可以看到配位水的化学位移比缔合水(即正常液体水)向低场移动近2ppm,这比通常在浓盐水溶液中观察到的差值提高了一个数量级。当[M~+]/[H_2O]大于100/1时,配位水的化学位移随阳离子不同而趋于不同的极限值,其顺序为NH_4~+(6.76)>Li~+(6.60)>Na~+(5.96)>K~+(5.40)。 从不同体系NMR图峰形和半高宽度Δv_(1/2)的变化,可以观察到阴离子的结构和组成对离子的水化作用有较大的影响。有关阴离子水合情况的研究工作正在进行中。
In this paper, a new method was developed by using anhydrous saponification extractant and water to form microemulsion to study ionic hydration. The changes of chemical shifts of water protons in acidic phosphonate D_2EHPA (alkali metal salt) -ROH- kerosene-water system were studied. To study the hydration of alkali metals, the results obtained and naphthenic acid system is similar. When [M ~ +] / [H_2O] changes from 100/1 to 1/100, it can be seen that the chemical shift of coordinated water moves nearly 2 ppm lower than that of associated water (ie, normal liquid water) The difference observed in the concentrated brine solution increased an order of magnitude. When [M ~ +] / [H_2O] is more than 100/1, the chemical shifts of coordination water tend to different limits with different cations, and the order is NH_4 ~ +6.76> Li ~ +6.60> Na ~ + (5.96)> K ~ + (5.40). From the change of the peak shape and the half-height width Δv_ (1/2) of the NMR spectra of the different systems, it can be observed that the structure and composition of the anion have a greater influence on the hydration of the ions. Research on the hydration of anions is underway.