288.15 K-323.15 K下氯化锂、硫酸锂溶液的密度及摩尔体积研究

用振荡管密度计测定了常压下,温度在288.15-323.15 K范围内不同离子强度的LiCl和 Li₂SO₄溶液的密度,计算了两种锂盐在不同温度下的表观摩尔体积,溶液的浓度范围分别为(0.1~18.9) mol·kg-1及(0.03~3.0)mol·kg-1。用Pitzer离子相互作用模型拟合了LiCl和Li₂SO₄不同温度下的的Pitzer单电解质体积参数,模型的计算值与实验值相吻合良好。     

Pitzer模型对盐湖卤水体系Li+-K+-Mg2+-SO2-4-H2O273.15 K时溶解度的预测

利用文献报道的单盐溶液水的渗透系数,结合Pitzer方程,进行了Li₂SO₄-K₂SO₄-MgSO₄-H₂O体系的参数化工作,得到了273.15 K和298.15 K Li₂SO₄、K₂SO₄、MgSO₄的单盐参数以及二离子和三离子相互作用参数。利用已获得的参数对Li₂SO₄-MgSO₄-H₂O体系、Li₂SO₄-K₂SO₄-H₂O体系、K₂SO₄-MgSO₄-H₂O体系273.15 K的溶解度进行了预测,并与已有的实验数据进行了比较,获得了比较满意的结果。首次利用Pitzer模型对Li₂SO₄-K₂SO₄-MgSO₄-H₂O体系273.15 K的溶解度进行了预测,可靠的理论预测结果减少了繁重的实验测定工作。     

288.15 K-323.15 K下四硼酸锂溶液的体积性质（英文）

用振荡管密度计测定了常压下288.15 K～323.15 K范围内不同浓度的Li_2B_4O_7溶液的密度,计算了其在不同温度下的表观摩尔体积。用Pitzer离子相互作用模型拟合了Li_2B_4O_7在不同温度下的Pitzer单电解质体积参数,模型的计算值与实验值相吻合良好。     

六元体系Li–Na–K–Mg–Cl–SO4–H2O多温相平衡预测

采用基于扩展UNIQUAC模型的AQSOL027软件针对水盐体系Li–Na–K–Mg–Cl–SO₄–H₂O的六个五元子体系进行相平衡理论计算,首次报道了多个五元子体系在多个温度条件下的相图,将计算相图与已有实验相图以及基于其它热力学模型的计算相图进行了比较。结果表明：AQSOL027在相图计算中具有较好的准确性和可靠性。AQSOL027是一款基于Excel、用于计算复杂多温水-盐体系Li–Na–K–Mg–Ca–H–Cl–(HSO₄/SO₄)–(CO₂/HCO₃/CO₃)–(H₃BO₃/B₄O₇/BO₂)–OH–H₂O的计算机软件,集成了扩展UNIQUAC模型和相平衡算法,该软件可结合SysCAD和Aspen过程模拟器,实现盐田工艺过程的计算机辅助设计。     

Recent Progress on Structure of Aqueous Polyborate Solutions

The crystal structure of metal borates has been extensively investigated by X-ray and neutron diffraction,but,the structure of aqueous polyborate solutions are still largely unknown.Over the last decade,our group has focused on studying the structure of complex aqueous polyborate solutions of Li,Na,K,Rb,Cs,and Mg using synchrotron radiation X-ray scattering(XRS),EXAFS,Raman,NMR,and DFT,as well as determining the density,conductivity and pH of such solutions.Polyborate species distributions were calculated using pH measurements,and the main species in the solution have been confirmed by NMR and Raman spectra.For alkali-metal metaborates,the dominant species is always B(OH)-₄in a wide range of concentration,while the presence of others species is negligible.For alkali metal tetraborates,when concentration is in the extreme low range,only B(OH)₃ and B(OH)-₄ are present in these solutions.As the total boron concentration increases,B(OH)₃ and B(OH)-₄ polycondensated to form more complex oligomers.Of them,while B₄O₅(OH)2-₄ in the tetraborate solutions is the main species,B(OH)₃,B(OH)-₄,and B₃O₃(OH)-₄ are minor species,and B₃O₃(OH)2-₅ and B₅O₆OH)-₄ are present only in negligible amounts.As solution continues to concentrate,B₄O₅(OH)2-₄ eventually becomes the dominant species,which is consistent with the congruent compound M₂B₄O₇·nH₂O(M=Li,Na,K,Rb,Cs) in the system M₂O-B₂O₃-H₂O(M=Li,Na,K,Rb,Cs).For alkali metal pentaborates,B(OH)₃ and B(OH)-₄ are the main species at low concentrations.The species distribution,Raman and NMR spectroscopy results verified that the dominant species in concentrated pentaborate solutions with Li and Na is pentaborate B₅O₆OH)-₄,but it is surprising that the main species with K,Rb,and Cs is always the triborate monoanion B₃O₃(OH)-₄.Although all M[B₅O₆OH)₄]·nH₂O(M=Li,Na,K,Rb,Cs) are all congruent compounds in the system M₂O-B₂O₃-H₂O(M=Li,Na,K,Rb,Cs) ,the main species in aqueous solutions are quite different because of various cation hydration distance(d),hydration number(CN),and configuration,especially charge(Z).For bivalent Mg²⁺,three borate minerals,namely,Inderite(2MgO·3B₂O₃·15H₂O),Hungchaoite(MgO·2B₂O₃·9H₂O),and Mcallisterite(MgO·3B₂O₃·7.5H₂O),exist in the system MgO-B₂O₃-H₂O at 298K.Inderite is a congruent compound,but Hungchaoite and Mcallisterite are incongruent compounds.The species distribution and Raman spectra demonstrat that the predominant species in all the solutions with magnesium borates is bivalent triborate B₃O₃(OH)2-₅,while the subordinate species are B(OH)-₄ at a low B₂O₃/MgO ratio and B(OH)₃at a high B₂O₃/MgO ratio,and the other anions are negligible,as the high Z of the borate anion must match that of Mg²⁺.The disappearance of divalent B₄O₅(OH)2-₄ is in agreement with its incongruent nature.The DFT and XRS results showed that tetrahedral Li(H₂O)⁺₄(d=0.20 nm,CN=4),octahedral Na(H₂O)₆⁺(d=0.236 nm,CN=6),and Mg(H₂O)²⁺₆(d=0.210 nm,CN=6) in the first hydration shell belong to Platonic polyhedra.However,K(H₂O)⁺₈(d=0.28 nm,CN=8,XRS and DFT),Rb(H₂O)⁺₈(d=0.293 nm,CN=7.7-8.2,EXAFS),and Cs(H₂O)⁺₈(d=0.320-0.326 nm,CN=7.6-7.9,EXAFS) are inclined Voronoi polyhedra.Therefore,the effects of cation Z and d on the structure of polyborates in aqueous solutions are deterministic,while the effect of hydrated-cation symmetry is secondary.Their hydrolysis order was:Mg＞Li＞Na＞K＞Rb＞Cs,in step with hydration power.Among them,Mg²⁺ and Li⁺have a strong tendency towards hydrolysis,but Na⁺ scarcely hydrolyzes,especially Rb⁺ and Cs⁺ have a little protonation.X-ray scattering of aqueous alkaline sodium borohydride solutions confirmed that dihydrogen bonds exist in an aqueous solution.The four distinct features of dihydrogen bonds in aqueous solution-unidirectionality,divaricativity,multicentricity,and multidentativity have been also described here in brief.     

四元体系Li2SO4+Na2SO4+K2SO4+H2O298.2 K相平衡研究

为了获取锂钠钾共存硫酸盐体系298.2 K下各盐结晶形式,采用等温溶解平衡法研究了298.2 K下四元体系Li₂SO₄₊Na₂SO₄₊K₂SO₄₊H₂O的相平衡关系,测定了该体系的溶解度和密度,采用X-ray粉晶衍射法测定了平衡固相组成,并绘制了相应的稳定相图和多温对比图。研究表明,298.2 K下该四元体系为复杂四元体系,有复盐2Li₂SO₄·Na₂SO₄·K₂SO₄、Li₂SO₄·3Na₂SO₄·12H₂O、LiKSO₄、Na₂SO₄·3K₂SO₄生成。其稳定相图由6个四元共饱点、12条单变量曲线以及7个结晶区组成。其中,复盐Na₂SO₄·3K₂SO₄结晶区最大,表明其在该体系中最易结晶析出;Li₂SO₄·H₂O结晶区最小。对比273.2 K、288.2 K、298.2 K、323.2 K、373.2 K四元体系多温相图可知,273.2 K时未发现复盐Na₂SO₄·3K₂SO₄和2Li₂SO₄·Na₂SO₄·K₂SO₄结晶形式;Na₂SO₄·10H₂O和Li₂SO₄·3Na₂SO₄·12H₂O结晶形式在323.2 K和373.2 K时转变为Na₂SO₄和Li₂SO₄·Na₂SO₄。288.2~373.2 K时随温度升高,K₂SO₄和Na₂SO₄·10H₂O结晶相区减小,Li₂SO₄·H₂O、Na₂SO₄、LiKSO₄和Li₂SO₄·Na₂SO₄结晶相区增大;Na₂SO₄·3K₂SO₄结晶相区先增大后减小,在298.2 K时结晶相区最大;2Li₂SO₄·Na₂SO₄·K₂SO₄结晶相区先减小后增大,298.2 K时结晶相区最小。     

内蒙古西部地区盐湖水化学特征

2008年9~10月和2009年9月对内蒙古西部地区14个盐湖进行了考察、采样和分析。研究发现,本区盐湖卤水主要离子含量顺序为Na⁺>Cl->SO2-₄>Mg²⁺>K⁺,次要离子为Ca²⁺ >HCO-₃>CO2-₃,微量元素为B₂O₃>Br->Li⁺。Na⁺的分布特征为东部高,北部中等,西南部偏低;而Cl-为东高西低;K⁺大致为南高北低;Mg²⁺为中部高,西部低,北部与南部中等。SO2-₄、 Ca²⁺和CO2-₃的区域分布特征均不明显;微量元素Li⁺ 、Br-、B₂O₃含量虽局部(两大沙漠连接带)有所富集,但绝对含量不高。对天然盐湖和人工采盐池的卤水进行了对比。采盐池中卤水因为蒸发强烈,离子浓度显著高于天然盐湖。分析天然盐湖与采盐池卤水离子浓度的变化规律发现,卤水蒸发初期Na⁺、Cl-、SO2-₄离子浓度随矿化度的升高而增大,Ca²⁺离子浓度明显下降,卤水蒸发后期Mg²⁺、K⁺大量富集,整个卤水蒸发过程中微量元素Li⁺与B₂O₃浓度一直随矿化度的升高而增大。这些结果对内蒙古西部盐湖的研究与开发都具有积极意义。     

Mg(BO2)2在MgSO4和MgCl2-MgSO4水溶液中分解的相平衡与物种化学平衡

硫酸镁亚型盐湖老卤是MgCl₂、MgSO₄的饱和溶液体系,富集了Mg、B、Li等元素。本文针对含硼水盐体系热力学难以表达的问题,开展了硼在水盐体系存在形态及其平衡关系的研究。利用易于水解的Mg(BO₂)₂作为硼源,借助拉曼光谱和X射线衍射(XRD)为检测手段,定量研究Mg(BO₂)₂在MgSO₄-H₂O、MgSO₄-MgCl₂-H₂O体系中水解硼物种转化规律。结果表明:(1)Mg(BO₂)₂在MgSO₄溶液中的水解固相为MgB₂O(OH)6、MgB₄O₇·9H₂O和Mg(OH)₂;在MgSO₄-MgCl₂-H₂O溶液中水解固相为Mg₂B₆O₁₁·15H₂O、MgB₄O₇·9H₂O、Mg₂Cl(OH)₃·4H₂O。(2)Mg(BO₂)₂在MgSO₄溶液中水解,液相硼物种主要有B₃O₃(OH)-₄、B₃O₃(OH)₅2-、B(OH)-₄、B₄O₅(OH)₄2-、H₃BO₃,其分布受MgSO₄浓度影响很大,MgSO₄浓度从0增加至饱和,B₃O₃(OH)-₄始终占总硼量的50.07%以上,B₃O₃(OH)₅2-占液相总硼从4.77%上升至37.16%为第2化学物种。(3)在MgSO₄-MgCl₂-H₂O溶液中,硼物种的主要形态有B₃O₃(OH)-₄、B₃O₃(OH)₅2-、B(OH)-₄,其分布 随[Cl₂2-]/([Cl₂2-]+[SO₄2-])变化很大,在MgCl₂和MgSO₄的共饱溶液中,分别占液相总硼量的58.91%,14.62%和12.81%。(4)液相硼物种之间平衡关系的活度商lnQ,不仅与溶液pH、水活度有关,还与MgSO₄、MgCl₂摩尔浓度呈二元线性关系,这样就可将硼在H₃BO₃-NaOH体系物种分布关系的lnQ扩展到 (MgSO₄,MgCl₂,MgSO₄-MgCl₂)水溶液的多元体系。由此获得硼物种的量化关系,可为推算硼在水盐体系的物种分布,进而计算含硼电解质溶液热力学性质提供依据。     

288.15～323.15 K下氯化锂、硫酸锂溶液的密度及表观摩尔体积研究（英文）

用振荡管密度计测定了常压下,温度在288.15-323.15K范围内不同离子强度的LiCl和Li_2SO_4溶液的密度,计算了两种锂盐在不同温度下的表观摩尔体积,溶液的浓度范围分别为(0.1~18.9)mol·kg-1及(0.03~3.0)mol·kg-1。用Pitzer离子相互作用模型拟合了LiCl和Li_2SO_4不同温度下的的Pitzer单电解质体积参数,模型的计算值与实验值相吻合良好。     

中图分类号：O642.3 文献标识码：A 文章编号：

不同形态硼酸盐焓、熵、吉布斯自由能等热力学参数极为缺乏,其准确测定对丰富和发展盐湖硼酸盐化学理论至关重要。本文采用TAM IV微量热计测定了五水合五硼酸钠(NaB₅O₈.5H₂O)溶解热。根据设计的热化学循环,结合Pitzer电解质模型和热力学基本公式,首次获得了NaB₅O₈.5H₂O在298.15 K下标准生成焓(, -5189.4820 kJ×mol^_-1)、标准生成熵(, 4380.4771 kJ×mol^_-1)、标准生成吉布斯自由能(, 4380.4771 kJ×mol^_-1)等热力学参数。这些尚未见报道的热力学参数对丰富无机盐热力学数据和促进盐湖资源综合利用具有重要的科学价值。     

三元体系Na2B4O7—NaHCO3—H2O和Na2CO3—NaBO2—H2O等温溶解研究

作为研究四元体系Na2B4O7-Na2CO3-NaHCO3-NaBO2-H2O的开端，测定了三元体系Na2B4O7-NoHCO3-H2O和Na2CO3-NaBOH2-H2O在0℃，15℃，45℃时的溶解度，绘制了相应的组成－性质图。两个三元体系的溶度图在研究温度范围内均属于低共饱型，平衡固相为组分化合物或其水合物。     

NH4Cl-CaCl2-H3BO3-H2O体系中H3BO3介稳区性质的研究

为探究南翼山油田水中NH_4Cl对H_3BO_3低温介稳区性质的影响,采用浊度法测量了253.15 K～303.15 K温度范围不同浓度的NH_4Cl对CaCl_2溶液中硼酸的溶解度影响和介稳区宽度;依次根据Nyvlt自洽方程理论求得成核级数m、经典三维成核理论求得固—液界面能γ,实验结果表明,CaCl_2溶液中的NH_4Cl对H_3BO_3溶解度影响很小;CaCl_2溶液中H_3BO_3的介稳区宽度随着NH_4Cl浓度的增加先变小后变大,氯化铵质量分数在0.12%～1.13%之间存在着一个临界值,此时硼酸的介稳区宽度最小。     

Stacking for the frequencies and Qs of 0S0 and 1S0

Summary. Using nine IDA records for the Indonesian earthquake of 1977 August 19, we have formed an optimal linear combination of the records and have measured the frequency and Q of ₀ S ₀ and ₁ S ₀. The frequency was measured using the moment ratio method. The attenuation was measured by the minimum width method and by the time-lapse method. The frequency and attenuation were measured simultaneously by varying them to obtain a best fit to the data. A 2000-hr stack, the sum of nine individual records, for ₀ S ₀ gave a frequency of 0.814664 mHz±4 ppm. The values for the Q of ₀ S ₀ for the three different methods of measurement were 5600,5833 and 5700, respectively. The error in the estimates of Q ^-1 is about 5 per cent for the minimum power method. For ₁ S ₀ a 300-hr stack yielded a frequency of 1.63151 mHz±30 ppm. The values of Q for this mode were 1960, 1800 and 1850, respectively, with an error in Q ^-1 of about 12 per cent for the minimum power method.     

Li+,Na+,K+/Cl-,SO2-4-H2O五元体系25 ℃相图及其应用

Li⁺,Na⁺,K⁺/Cl-,SO2-₄-H₂O五元体系相图对于硫酸钠亚型富锂卤水分离提取锂盐、锂辉石加工利用和锂盐产品的开发利用工艺制定都有指导作用。20世纪50年代曾有人研究过这一体系25 ℃时的相图,限于当时的科研水平,液相组成确定不准确,对平衡固相的判断,后来诸多研究结果证明也有错误。50多年来再没有人研究这一五元体系相图。利用我们提出的Li⁺,Na⁺,K⁺/Cl^-,SO^2-₄-H₂O六元体系热力学模型,对该五元体系的平衡溶液组成和正确的平衡固相进行理论预测,给出了该体系的完整相图。结合硫酸锂混盐分离、加工实例阐述了该五元体系相图的应用。     

MgCl2-CaCl2-H2O体系多温下的体积性质研究

溶液的体积性质是工业生产中常用的控制参数,也是深层海水、盐湖卤水等天然水体系的研究所需要关注的。通过实验测量和Pitzer离子相互作用模型相结合的方法研究了283.15～323.15 K下MgCl_2-CaCl_2-H_2O混合溶液在不同离子强度(I=4.5,9.0,13.5 mol·kg~(-1))下的体积性质,包括混合溶液的密度、表观摩尔体积和超额体积,并用Pitzer离子相互模型拟合了MgCl_2-CaCl_2-H_2O混合溶液的体积参数。模型的密度计算值和实验值的差值均在±4×10~(-3) g·cm~(-3)以内,表明模型的计算值和实验值吻合良好。