Vapor-Liquid Equilibria of the FeSO4-Fe-2(SO4)(3)-H2SO4-H2O System at (30, 60, 90, and 101.3) kPa
Vapor-Liquid Equilibria of the FeSO4-Fe-2(SO4)(3)-H2SO4-H2O System at (30, 60, 90, and 101.3) kPa
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FeSO4-Fe-2(SO4)(3)-H2SO4-H2O 体系在 (30、60、90 和 101.3) kPa 下的汽液平衡
DOI：
10.1021/je5010142
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发表时间：
2015
影响因子：
--
通讯作者：
Li Zhibao
中科院分区：
文献类型：
--
作者：
Zhang Yan;Li Zhibao
采用准静态沸点计法测定了FeSO 4-Fe 2（SO 4）3-H2SO 4-H2O体系在（30、60、90和101.3）kPa下的汽液平衡（沸点）数据。发现沸点随着盐和酸的浓度增加而增加。利用Helgeson方程预测的三价铁离子（FeSO 4+，Fe（SO 4）2-，FeHSO 42+）的热力学数据（Δ Gf，298.15K0，Δ Hf，298.15K0和Sf，298.15K0），采用混合溶剂电解质（MSE）模型建立了该体系的综合热力学模型。通过回归实验沸点和文献中的Fe 2（SO 4）3-H2SO 4-H2O体系的化学计量渗透系数，确定了模型参数。对于Fe_2（SO_4）_3-H_2SO_4-H_2 O和Fe_2（SO_4）_3-H_2SO_4-H_2 O体系，回归沸点与实验值的平均绝对偏差分别为（0.30和0.36）K，而化学计量渗透系数的平均相对偏差仅为0.80%。新获得的参数的模型被用来预测分布的含铁物种（Fe 3+，FeSO 4+，Fe（SO 4）2-，和FeHSO 42+）作为温度和铁浓度的函数。此外，从文献中获得的Fe（III）/Fe（II）的氧化还原电位与通过新获得的参数计算的ln（aFe 3 +/aFe 2+）的曲线是直线，表明参数的良好性能。
Vapor–liquid equilibrium (boiling point) data of the FeSO4–Fe2(SO4)3–H2SO4–H2O system were measured by the quasi-static ebulliometric method at (30, 60, 90, and 101.3) kPa. The boiling points were found to increase with increasing concentrations of both the salts and the acid. By use of the thermodaynamic data (ΔGf,298.15K0, ΔHf,298.15K0, andSf,298.15K0) of ferric complex ions (FeSO4+, Fe(SO4)2–, and FeHSO42+) predicted by Helgeson’s equation, a comprehensive thermodynamic model for the system was developed with the mixed-solvent electrolyte (MSE) model. Model parameters were determined via regressing our own experimental boiling points and the literature stoichiometric osmotic coefficients (ϕst) of the Fe2(SO4)3–H2SO4–H2O system. The average absolute deviations between the regressed boiling points and the experimental data were found to be (0.30 and 0.36) K for the Fe2(SO4)3–H2SO4–H2O and FeSO4–Fe2(SO4)3–H2SO4–H2O systems, respectively, while the average relative deviation for the stoichiometric osmotic coefficient was only 0.80 %. The model with newly obtained parameters was used to predict the distribution of iron-bearing species (Fe3+, FeSO4+, Fe(SO4)2–, and FeHSO42+) as functions of temperature and iron concentration. In addition, plots of the redox potential of Fe(III)/Fe(II) obtained from the literature versus ln(aFe3+/aFe2+) calculated by the newly obtained parameters are straight lines, indicating the good performance of the parameters.