298.15K下Li2SO4-Li2B4O7-H2O体系热力学性质的等压研究

用等压法研究了Li2SO4-Li2B4O7-H2O体系的Li2SO4和Li2B4O7纯盐水溶液(离子强度范围分别为0.3577~5.6378 mol.kg-1及0.1747~2.4497mol.kg-1)及混合盐水溶液(离子强度范围为0.3118~5.5248mol.kg-1)的渗透系数,并获得了该体系渗透系数随离子强度的变化规律。用实验数据以最小二乘法求取了Li2SO4和Li2B4O7的纯盐参数及混合盐参数,拟合的标准偏差分别为0.0072和0.0188。用Pitzer模型计算的渗透系数与实验值结果取得一致,表明该模型能够较好的描述25℃下Li2SO4-Li2B4O7-H2O体系的热力学性质。实验对完善含锂、硼盐湖卤水体系的热力学模型和盐湖资源的综合开发具有重要意义。     

273.15K下LiCl-Li2B4O7-H2O体系热力学性质的等压研究

用等压法研究了273 15K下LiCl-Li2B4O7-H2O体系中纯盐水溶液(离子强度范围为LiCl0 2046～2 5055mol·kg-1,Li2B4O70 1295～0 3700mol·kg-1)以及混合盐水溶液(离子强度范围为0 0931～2 4911mol·kg-1)渗透系数和水活度;计算了LiCl-Li2B4O7-H2O体系的饱和蒸汽压,获得饱和蒸汽压、渗透系数随离子强度的变化规律。用实验数据以最小二乘法求取了LiCl和Li2B4O7纯盐参数及体系的混合盐参数,拟合的标准偏差分别为0 0077和0 026。用该模型计算的渗透系数值与实验结果取得合理的一致。同时研究结果与273 15K下LiCl-Li2SO4-H2O体系的渗透系数随离子强度变化的规律作了比较。本研究对完善低温下含锂、硼盐湖卤水体系的热力学模型和盐湖资源的综合开发利用具有重要意义。     

298.15K下LiCl-Li_2B_4O_7-H_2O体系中LiCl的活度系数和离解平衡研究

用锂离子选择电极和经典 Ag- Ag Cl电极测定了 2 98.15K下 L i Cl- Li2 B4 O7- H2 O体系中离子强度范围为 0 .0 1～ 2 .50 mol· kg-1,不同 Li2 B4 O7离子强度分数的 L i Cl的平均活度系数。由实验数据 ,用迭代法及多元线性回归法 ,求取了 L i2 B4 O7的化学计量离解平衡常数 Km,热力学离解平衡常数 K及 Pitzer离子作用参数 ,并与实验值比较标准偏差为 0 .0 50 0。同时该实验结果在 0 .0 1- 0 .50 mol·kg-1离子强度范围内与 2 98.15K下 L i Cl- L i2 SO4 - H2 O体系 L i Cl平均活度系数的变化趋势进行了比较 ,得到 L i Cl在 Li2 B4 O7介质中平均活度系数随 Yb的增大而增大 ,而在 L i2 SO4 介质中则减小     

K2B4O7的Pitzer参数的计算

由于硼酸盐在电解质中的特殊性 ,硼酸盐的热力学问题一直被化学家所重视。根据文献数据 ,经多种处理获得K2 B4 O7不同存在形式的硼氧配阴离子的Pitzer纯盐参数、K2 B4 O5(OH) 4电离化学计量平衡常数Km。采用所获得的Pitzer纯盐参数计算K2 B4 O7不同存在形式的硼氧配阴离子的渗透系数 ,并与表观实验值进行比较     

Rb2Ca[B4O5(OH)4]2·8H2O溶解及相转化过程的研究

利用IR光谱和Raman光谱等实验手段,对25℃时Rb2Ca[B4O5(OH)4]2·8H2O的溶解及相转化过程进行了初步探索,结果表明,Rb2Ca[B4O5(OH)4]2·8H2O溶于水后,硼在溶液中主要以B(OH)3和[B(OH)4]-的形式存在,残留固相由开始的无定形水合三硼酸钙,最终部分转变为Ca2[B3O3(OH)5]2·8H2O晶体。     

323.15K下LiCl-Li2SO4-H2O体系热力学性质的等压研究

在50℃下用等压法研究了LiCl和Li2SO4的纯盐水溶液(浓度范围分别为0 8～8 1mol·kg-1,0 7～3 1mol·kg-1)以及LiCl-Li2SO4-H2O混合体系(离子强度范围为1 0～8 6mol·kg-1)的渗透系数和水活度等热力学性质,并与0℃,25℃的数据做了对比,揭示了渗透系数随离子强度、温度及Li2SO4离子浓度分数之间的变化规律。Zdanovskii规则非理想溶液表达式和扩展式可以用来描述该体系等压平衡浓度之间的关系。根据Pitzer离子相互作用模型对实验数据进行了理论分析,拟合求取了50℃下该体系的纯盐参数和混合参数,计算值和实验值相吻合,表明Pitzer模型能够较好的描述50℃下该体系的热力学性质。     

25℃时K2B4O7-H2O体系的离子相互作用模型研究

根据硼酸盐水溶液中硼浓度不同时硼物种之间形成多种聚合与解聚的平衡反应理论和光谱学研究结果,利用已有的该体系25℃等压实验数据,拟合获得了该体系的两个化学计量平衡常数、各种硼氧配阴离子单一的以及二离子和三离子之间的相互作用Pitzer参数,确定了该体系在不同总硼浓度范围内各种硼氧配阴离子的存在形式与定量分布,将所获得的离子相互作用模型计算出的渗透系数与实验值进行了比较,获得了令人满意的结果。     

五硼酸钾溶液中含硼物种分布研究

采用物种分布图和核磁共振实验研究了五硼酸钾溶液中含硼物种的类型、含量和溶液浓度间关系。研究表明五硼酸钾在稀溶液中几乎全部水解为B(OH)3和B(OH)4-;在较浓溶液中主要物种为B3O3(OH)4-和B(OH)3,而B5O6(OH)4-和[B4O5(OH)42-]的含量较小。核磁共振实验研究给出了B(OH)4-, B3O3(OH)4-和B5O6(OH)4-的生成常数K1, K3, K5,研究得出B5O6(OH)4-含量很少的原因是其解聚为其它类型硼酸根离子。外加离子促进五硼酸根离子的生成,而高温条件促进B5O6(OH)4-发生解聚反应。     

LiB_5O_8溶液物理化学性质研究

根据Li2O-B2O3-H2O多温相图合成晶体LiB5O8·5H2O。在从稀到饱和浓度范围内测定LiB5O8水溶液在40℃和50℃下的物化性质(密度、粘度、电导率和p H),并根据相应的模型进行关联。根据文献的化学平衡常数以及测定的p H值,计算出硼酸盐溶液中存在的B(OH)3、B(OH)-4、B3O3(OH)-4、B4O5(OH)2-4和B5O6(OH)-4等物种各浓度下的摩尔分数,并给出溶液中可能存在的反应及其相应的机理。     

四元体系KCl-K2SO4-KBO2-H2O在298.15 K的Pitzer模型研究

在Pitzer电解质溶液理论的基础上采用两种模型计算了KCl-K₂SO₄-KBO₂-H₂O体系及其子体系的溶解度。模型I假设溶液中只有一种硼物种B(OH)₄-,模型II假设溶液中有4种硼物种,分别对应于B(OH)₃、B(OH)₄-、B₃O₃(OH)₄-和B₄O₅(OH)₄2-。模型I与模型II的溶解度计算结果接近,且与实验值吻合较好。采用模型II计算了上述体系溶液中的硼物种和OH-的浓度。各硼物种的浓度主要受溶液中总硼浓度的影响,而很少受KCl和K₂SO₄的影响。计算结果说明在计算偏硼酸钾溶液体系溶解度时,可近似认为溶液中硼物种只有B(OH)₄-。模型II可用于计算含偏硼酸钾体系的pH值。本文的计算结果可为复杂偏硼酸钾体系模型的构建提供理论基础。     

三元体系K+,Mg2+/B4O2-7-H2O 25℃相关系研究

对三元体系K+,Mg2+/B4O2-7-H2O25℃的溶解度进行了研究,该体系属简单共饱型,两段溶解度曲线对应于体系的两种原始组分K2B4O7·4H2O、MgB4O7·9H2O的结晶区,共饱点组成为K2B4O713 96%,MgB4O70 53%。     

A Raman Investigation on the Boron form Occurring in Salt Lake Brine during Evaporation

Boron resources are abundant in the Da Qaidam Salt Lake of the Qaidamu basin in China,which has generated significant attention due to the presence of polyborate species in brine from this lake. In this study,Raman spectroscopy was used to investigate the existing form of boron in brine during evaporation. MgO·2 B_2 O_3-H_2 O,MgO·2 B_2 O_3-MgCl_2-H_2 O,and MgO·2 B_2 O_3-MgSO_4~-H_2 O solutions were also studied to determine the influence of boron concentration,pH,and electrolytes on the borate speciation from brine. The mononborates B( OH)_3 and B( OH)_4~-were found to be the only forms present in natural salt lake brine. Brine evaporation promoted the formation of the polyborate anions B_3 O_3( OH)_4~-,B_5 O_6( OH)_4~-,and B_6 O_7( OH)_6~(2-)and also promoted the disappearance of the B( OH)_4~-ion from brine at boron concentrations of more than 11 g/L B_2 O_3. The pentaborate ion B_5 O_6( OH)_4~-was sensitive to the solution pH and appeared only at p H values less than 8. 0. Meanwhile,the hexaborate ion B_6 O_7( OH)_6~(2-)was observed to be more dependent on the electrolyte magnesium chloride due to its special properties,such as promoting boron accumulation,lowering solution pH,and also its strong affinity for water molecules,which were all beneficial for the polymerization of borate ions in brine. Interaction mechanisms between polyborate anions during evaporation are also proposed herein. ake; evaporation; polyborate species; interaction mechanism.     

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.     

五硼酸钾水溶液的差示FT-IR和Raman光谱研究

研究了KB5O8·4H2O水溶液20℃时的差示FT-IR光谱和Raman光谱,对振动频率进行了归属。探讨了KB5O8·4H2O水溶液中硼氧配阴离子的存在形式(主要是B(OH)3、[B3O3(OH)4]-和[B5O6(OH)4]-)和相互作用。     

盐卤硼酸盐化学ⅩⅤⅢ·MgO·3B_2O_3-MgCl_2-H_2O浓溶液中六硼酸镁盐结晶动力学

人工模拟合成B_2O_3/MgO=3的过饱和氯化镁溶液,分别在20～60℃恒温条件下,在密封、无外界扰动条件下进行水合六硼酸镁盐结晶动力学实验测定。最后分离固相,经处理后,用化学分析和物理分析法进行物相鉴定。采用计算机对实验数据进行处理,给出相应的结晶动力学方程。根据硼在水盐溶液中是以多粒子形式共存这一结论,提出不同水合六硼酸镁盐的结晶反应机制。     

Solid-Liquid Phase Equilibria in the Aqueous System Containing Potassium, Magnesium, and Borate at 308.15 K

Experimental studies on the solubility,density,refractive index,and pH value in the aqueous system containing potassium,magnesium,and borate at 308. 15 K were determined with the method of isothermal dissolution equilibrium. Based on the experimental results,the diagrams of solubility,density,refractive index,and pH value in this system were plotted. We found that there were one eutectic point and two crystallization regions corresponding to the large area of inderite( L + Mg_2 B_6 O_(11)·15 H_2 O) and the relatively small area of potassium borate tetrahydrate( L + K_2 B_4 O_7·4 H_2 O),respectively. Neither double salt nor solid solution was found in this system. The physicochemical properties( density,refractive index,and pH value) in solution at 308. 15 K changed regularly with increasing potassium borate concentration. The calculated values of density and refractive index using empirical equations of the aqueous system were in good agreement with the experimental values.