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本文测定了KCIO_3,NaNO_2,NaNO_3三种盐在甲醇—苯,甲醇—甲苯,甲醇—环己烷,甲醇—四氯化碳和甲醇—1,4—二氧六环以及KCJ在甲醇—苯和甲醇—甲苯中溶解度,与非电解质的摩尔分数X_(Ne)的关系符合经验公式log(s_o/s_m)=kX_(Ne),其中s_o和s_m分别为盐在纯甲醇和混合溶剂中的溶解度。同时得到了与非电解度体积分数φ_(Ne)的经验公式log(s_o/s_m)=k_φφ_(Ne),其中K_φ称为第二介质常数。盐的溶剂化数近似地符合公式n_++n_=-2 log(s_o/s_m)/logφ_P。本文从改进的Born公式,推导出第二介质参数k′的理论计算公式 k’=Ne~2/2.303×4RT(1/r_++_++1/r_-+_)D_o-D_(Ne)/D_o~2式中N为Avogadro常数,e为电子电量,R和T具有通常意义,γ_+和γ_-分别为正负离子的晶体半径,_+和_-分别为正负离子在溶液中的半径比晶体半径为大的增量,D_o和D_(Ne)为甲醇和非电解质的介电常数。计算的k′和实验的k_φ数值相近,k′对k_φ有一定的预示。
In this paper, three kinds of salts of KCIO_3, NaNO_2 and NaNO_3 were determined in methanol-benzene, methanol-toluene, methanol-cyclohexane, methanol-carbon tetrachloride and methanol-1,4-dioxane, The solubility of methanol in toluene, which is related to the molar fraction of Ne (NO), satisfies the empirical formula log (s_o / s_m) = kX_ (Ne), where s_o and s_m are the solubilities of salts in pure methanol and mixed solvents, respectively. At the same time, the empirical formula log (s_o / s_m) = k_φφ_ (Ne) and non-electrolytic volume fraction φ_ (Ne) are obtained, where K_φ is called the second dielectric constant. The solvatisation number of the salt approximates the formula n_ ++ n_ = -2 log (s_o / s_m) / logφ_P. In this paper, the theoretical formula of the second medium parameter k ’is deduced from the modified Born formula, k’ = Ne ~ 2 / 2.303 × 4RT (1 / r _ ++ _ ++ 1 / r _- + _) D_o-D_ ) / D_o ~ 2 Where N is the Avogadro constant, e is the electronic power, R and T have the usual meaning, γ_ + and γ_- are the crystal radius of positive and negative ions, respectively, _ + and _- positive and negative ions in solution Radius is larger than the crystal radius increment, D_o and D_ (Ne) for the methanol and non-electrolyte dielectric constant. Calculated k ’and experimental k_φ values are similar, k’ for k_φ have some predictions.