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不同浓度的Na2SO4水溶液的拉曼光谱显示了SO42-的四个拉曼活性带:980 cm-1处的SO42-的对称伸缩振动模式v1带,1 106 cm-1处的反对称伸缩振动模式v3带,448 cm-1处的变形振动模式v2带和617 cm-1处的变形振动模式v4带。482 cm-1处的肩膀峰是由于NaSO4-离子对的形成对448 cm-1的v2带的影响而形成的SO42-的一个新的振动峰。浓Na2SO4水溶液中,水共享离子对[Na+.H2O.SO42-]-是主要的离子对物种。随着Na2SO4水溶液浓度的增加,Na+和SO42-的相互作用增强,NaSO4-离子对所占的摩尔分数增加。 相似文献
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报道由硫酸钠水溶液实验径向分布函数通过理论模型计算,解析溶液结构参数的方法。其中包括建立理论结构模型的基本依据,专用KURLVR程序使用和结构参数最小二乘精修,以及高斯多峰拟合等实用方法,最终给出能够阐述溶液本质的微观结构参数。结果表明,硫酸钠溶液中水合Na+有2个水合层,第一水合层Na+-OH2(I)距离为0.243 nm,配位数6.0;第二水合层距离为0.448 nm,配位数为13.3;SO2-4存在第一水合层,SO2-4-H2O距离为0.374 nm,配位数为9.1;水合硫酸根原子团中氧原子与水分子的作用距离和配位数按OS-W(1)、OS-W(2)、OS-W(3)、OS-W(4),距离依次为0.283、0.322、0.375和0.486 nm,配位数除OS-W(2)为12.9,其余都在8左右;除此之外溶液中还存在NaOSO-3接触离子对,Na-S距离为0.348 nm,配位数0.20,与晶体结构比较证实SO2-4以单齿形式配位到Na+;水共享离子对Na+-W-SO2-4中Na-S距离精修为0.491 nm,配位数0.62。精修的R因子为0.16,表明获得了很好的精修结果。 相似文献
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梯度太阳能池技术在盐湖化工中是一种经济分离无机盐产品的方法,本文创新性的采用等温蒸发法,模拟四元体系(LiCl + NaCl + Li2SO4 + Na2SO4 + H2O)在75℃等温蒸发相平衡,指导太阳池深池积温分离提取锂盐产品。实验测定了溶解度和溶液密度、pH值等物化性质,并绘制了干盐相图、水图和物化性质组成图。在该四元体系干盐相图中包含3个四元共饱点,7条单变量蒸发曲线和5个结晶区,分别为NaCl,Na2SO4,复盐Li2SO4·Na2SO4,Li2SO4·H2O和LiCl·H2O。采用 Pitzer模型和改进的HMW公式,拟合出该四元体系在75℃时的Pitzer单盐参数、混合离子作用参数和平衡固相的热力学平衡常数,并计算给该四元体系的相图,计算相图和实验相图有较大区别。等温蒸发相图能真实的反应盐湖中盐类沉积规律,并对指导太阳池分离盐类具有重要指导意义。 相似文献
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在HCl In2 (SO4) 3 H2 O体系中 ,溶液表观总离子强度恒定为I=0 2、0 4、0 6、0 8、1 0、1 5mol·kg-1,硫酸铟在溶液中的表观离子强度分数恒定为yB =0 0 0、0 1 0、0 2 0、0 3 0、0 5 0和 0 70条件下 ,应用经典的电动势方法测定无液体接界电池 (A)在 2 78 1 5~ 3 1 8 1 5K温度范围内的电动势 :Pt,H2 (1 0 1 3 2 5kPa) |HCl(mA) ,In2 (SO4) 3 (mB) ,H2 O|AgCl Ag (A)根据测得电池 (A)的电动势数据 ,考虑到该体系存在硫酸的二级解离 ,应用数学迭代方法确定平衡体系氢离子的浓度 ,进而确定了混合溶液中HCl的活度系数γA。结果表明 ,HCl的活度系数服从扩展的Harned规则。 相似文献
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在HCl-NiSO4-H2 O混合溶液中 ,以标准氢电极和银—氯化银电极组成无液接电池 ,恒定溶液总离子强度I和NiSO4在溶液中的离子强度分数yB 的条件下 ,在 2 78 1 5~ 3 2 3 1 5K温度范围内测定下列电池的电动势Pt,H2 ( 1 0 1 3 2 5kPa) |HCl(mA) ,NiSO4(mB) ,H2 O|AgCl-Ag由于体系存在硫酸的二级解离 ,应用数学迭代方法确定平衡体系氢离子的浓度 ,计算了混合溶液中HCl的活度系数γA,结果表明 ,在溶液总离子强度保持恒定时 ,HCl的活度系数服从Harned规则。在溶液组成恒定时 ,盐酸的活度系数logγA 对热力学温度l/T作图 ,是一条直线 相似文献
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Isothermal Evaporating Phase Equilibria in the Quaternary System (LiCl+NaCl+Li2SO4+Na2SO4+H2O)at 348.15 K and 0.1 MPa:An Experimental and Theoretical Study 下载免费PDF全文
The gradient solar pond technique is an economic separating process employed in the inorganic chemical industrial production of salt lake chemical engineering processes. In this paper,a novel isothermal evaporation experimental method was employed to simulate the evaporation phase equilibrium for the reciprocal quaternary system( LiCl + NaCl + Li_2 SO_4+ Na_2 SO_4+ H_2 O) at 348. 15 K to serve as a useful guide for lithium salt production via the depth solar ponds. The isothermal evaporation equilibrium solubilities and physicochemical properties,including the densities and pH values,were experimentally investigated. The dry-salt phase diagram,water-phase diagram,and the diagram of the physicochemical properties versus composition were plotted with respect to the experimental data. The drysalt phase diagram consists of three invariant points,seven univariant solubility curves,and five crystallization regions,specifically halite( NaCl,Ha),thenardite( Na_2 SO_4,Th),double salt( Li_2 SO_4·Na_2 SO_4,Db_2),lithium sulfate monohydrate( Li_2 SO_4·H_2 O,Ls),and lithium chloride monohydrate( LiCl·H_2 O,Lc). Based on Pitzer and its extended HMW model,the Pitzer single salt parameters,mixing ion interaction parameters,and thermodynamic stable equilibrium constants for the quaternary system at 348. 15 K were obtained. The calculated phase diagram and experimental isothermal phase diagram at 348. 15 K exhibited a great difference. Based on these results,the isothermal evaporation phase diagram can truly reflect the salt sedimentary in salt lakes and can be applied as a useful guide for the solar pond process. 相似文献
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Li brines are the primary resources for Li salt industries. Evaporation is necessary to concentrate Li due to its low level of concentration in raw brines. The salt sequences during the evaporation of Li brines,especially the behavior of Li salts,represent key data for solar technologies. However,chemists cannot use any phase diagram to estimate Li salt sequences during evaporation at 25℃ . The thermodynamic model proposed by us in2003 represents the only tool for the prediction of equilibrium conditions during the evaporation of solutions containing Li~+,Na~+,K~+,Mg~(2+)/Cl~-,SO_4~(2-),and-H_2 O components at 25℃ . In this paper,the predicted salt sequences of 20 brines are reported. The results indicate that( 1) the first crystallized Li salt during evaporation of Li brine varies in brine composition;( 2) lithium sulfate is crystallized in many cases initially for brines of magnesium sulfate subtype,while Db4( Li_2 SO_4·K_2 SO_4) or Db3( 2 Li_2 SO_4·Na_2 SO_4·K_2 SO_4) appears first for sodium sulfate and magnesium sulfatesubtypes with lower Mg/Li composition,and the final eutectic point is H ~+ LiC ~+ Lc ~+ Ls ~+ Car;( 3) the final eutectic point is H ~+ LiC ~+ Lc ~+ Car for brines of chloride type; and( 4) Li content corresponding to the first crystallized Li salt is in the range of 0. 43%-1%. These findings enhance our knowledge of Li chemistry and provide insights into solar pond technology of the Li-brine process. 相似文献
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VLADISLAV TOMISIC VLADIMIR SIMEON Laboratory of Physical Chemistry Faculty of Science University of Zagre POB Zagre Croatia 《地理学报(英文版)》1993,(5)
Each eigenvector of the dispersion matrix[X]~T[X]was shown to be a partial predictor of the originaldata matrix [X],the sum of the predictions from the individual principal components being equal to theexpectance of [X].By comparing the distributions of the members of two neighbouring predictedmatrices,[X]_(1...i)and [X](1...i+1)(i.e.the sums of the first i and i+1 individual predictions respectively),it was shown that they should be indistinguishable provided that i is equal to or greater than the effectiverank of [X],and significantly different otherwise.This was confirmed by analysing the visible absorptionspectra of methyl orange and methyl red solutions as well as the Raman spectra of Na_2SO_4 and MgSO_4solutions.On the grounds of these findings,a non-parametric goodness-of-fit test for assessing theeffective rank of[X]was proposed which proved to be comparatively conservative and more robust thanmost currently used tests. 相似文献
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研究了三元体系Li~+,Mg~(2+)∥SO_4~(2-)—H_2O在25℃时的相关系和平衡液相的密度、粘度、折光率、电导等物化性质,该体系为简单共饱型,两段溶解度曲线对应于体系的两种原始组份Li_2SO_4·H_2O和MgSO_4·7H_2O的结晶区,无复盐和固溶体形成,亦无脱水作用发生,应用电解质溶液Pitzer模型检测该体系25C的溶解度,并用经验或半经验公式对平衡液相的密度和折光率进行了理论计算,计算值与实验值非常接近。 相似文献