离子液体([C_6MIm][TFSI])从体相电迁移至水相研究（英文）

离子在离子液体/水溶液二元系统中的电迁移行为在很多领域受到了越来越多的关注。本文通过研究不同条件下离子液体离子在电极液中的浓度变化,系统地研究了电极溶液酸—碱度,电极溶液中电解质浓度以及离子液体中溶解LiN (CF_3SO_2)_2与否对[C_6MIm]~+离子电迁移的影响。总的来说,随着电流的增加,[C_6MIm]~+离子向阴极水溶液的迁移量随之增加,向阳极水溶液的迁移量随之减少;然而N(CF_3SO_2)~-_2离子向阳极水溶液的迁移量随之增加,向阴极水溶液的迁移量随之减少。当电极溶液为碱性,[C_6MIm]~+离子的迁移量明显减少。在电极溶液中溶入LiN (CF_3SO_2)_2时或者将LiN (CF_3SO_2)_2溶入离子液体时,[C_6MIm]~+离子的迁移量也明显受到抑制。     

四苯硼钠—季铵盐质量滴定法分析钾含量研究

依据四苯硼钠—季铵盐容量法滴定K⁺离子的原理,采用质量滴定法,考察了滴定速度、松节油加入量对四苯硼钠与季铵盐反应的影响及共存离子(包括Li⁺、Mg²⁺、Ca²⁺、SO2-₄、B₄O2-₇、CO2-₃)对K⁺含量测定结果的影响。当测定K⁺离子含量在5～15 mg范围内,松节油最佳加入量为25滴,分析误差< 0.3%。     

Na+,K+,Rb+,Cs+//SO2-4-H2O体系固液相平衡热力学模拟

锂云母、铯榴石等矿物的硫酸盐焙烧浸出,是从中提取锂铷铯钾等碱金属元素的重要步骤,所得硫酸盐浸出液可近似看作Li⁺,Na⁺,K⁺,Rb⁺,Cs+ // SO₄2--H₂O六元水盐体系;其在浓缩过程呈现复杂的成盐特征,增加了各碱金属元素分离提取的难度,研究其相关水盐体系相图和相平衡性质对理解浸出液中碱金属的分离具有重要的理论指导意义。本文采用Pitzer-Simonson-Clegg超额Gibbs自由能方程和具有内在热力学一致性的CALPHAD方法,构建了Na⁺,K⁺,Rb⁺,Cs⁺//SO₄2--H₂O五元体系的多温固液相平衡热力学模型。借助该模型:1)实现了对Na₂SO₄₊Rb₂SO₄₊H₂O、Na₂SO₄₊Cs₂SO₄₊H₂O和K₂SO₄₊Cs₂SO₄₊H₂O三元体系的多温溶解度等温线的准确描述,并进一步构建了这些体系在240.15~380.15 K温度范围内的多温相图;2)实现了对K₂SO₄+Rb₂SO₄₊H₂O和Rb₂SO₄₊Cs₂SO₄₊H₂O体系中存在的固溶体相—水溶液平衡关系的准确描述,确认了(K,Rb)₂SO₄连续固溶体、以及(Rb,Cs)₂SO₄(α)和(Rb,Cs)₂SO₄(β)间断固溶体存在的合理性;3)预测了上述五元体系中所包含的全部4个四元子体系(Na₂SO₄₊ K₂SO₄₊ Rb₂SO₄+H₂O、Na₂SO₄ + K₂SO₄₊Cs₂SO₄₊ H₂O、Na₂SO₄₊ Rb₂SO₄₊Cs₂SO₄ + H₂O和K₂SO₄₊Rb₂SO₄₊Cs₂SO₄₊ H₂O)的相图,明确了四元相图中固溶体的类型及形成区域。然而,模型预测结果与现有四元体系实验数据间存在普遍的不一致性,尤其是固溶体形成区域,但模型预测结果从非实验角度给出了重要参考,对现有实验提出了挑战,未来对这些体系开展更为精细的实验研究非常必要。     

松嫩平原西部盐沼湿地水环境化学特征

松嫩平原西部盐沼湿地水环境碱化程度高,水中的pH值普遍高于8.0,多数为苏打钠型水。在对本区盐沼基本水环境化学特征阐述的基础上,通过对水化学的基本变量CO₃^2-、HCO₃^2-、Cl^-、Ca²⁺、Mg²⁺、SO₄^2-、Na⁺和派生变量(Cl^-+SO₄^2-)/HCO₃^2-及Na⁺/(Ca²⁺ Mg²⁺)等的相关分析,得出各水化学变量之间的相关关系,并以pH值为分类基础得到了判别函数和判别区域图,对区域盐沼湿地水环境化学特征的研究方法作出了有意义的尝试。     

拉果错盐湖卤水蒸发过程中Li+富集行为的分子动力学模拟

采用分子动力学模拟,研究了西藏拉果错盐湖卤水中阴、阳离子以及水分子间的相互作用行为。以盐湖卤水等温蒸发过程中粒子浓度变化的四个阶段为研究对象,分别计算了不同体系的扩散系数、配位数、均方位移和径向分布函数。计算结果表明,液相浓度越低时,H₂O分子对各离子之间的相互作用有抑制作用,液相中离子浓度越高时,SO₄2-易与CO₃2-竞争Li⁺形成离子对,从而影响盐湖卤水中Li⁺的富集。本文研究结果对盐湖卤水中Li⁺的迁移行为作出了机理解释,为盐湖卤水提锂的发展奠定了理论基础。     

KNO3溶液结构:密度泛函理论和分子动力学研究

基于密度泛函理论,采用ωB97XD方法和6-311++G(d,p)基组,系统研究了[K(H₂O)_n]⁺,[NO₃(H₂O)_n]-和KNO₃(H₂O)_n水合团簇的结构和性质;并结合经典分子动力学、OPLS-AA全原子力场以及SPC/E水模型模拟了不同水盐比(WSR) KNO₃溶液,目的在于深入理解KNO₃溶液中K⁺和 NO-₃的微观水合结构,以及K⁺-NO-₃离子间缔合作用特征。研究发现,对于KNO₃(H₂O)_n (n=6,8,10和12)水合团簇,K⁺第一水合层稳定结构为四、五和六水合结构,其中五水合结构最稳定。K⁺和NO-₃主要以溶剂共享离子对形式存在。随着团簇尺寸减小,直接接触离子对(CIP)物种出现。同时,分子动力学模拟证实KNO₃溶液中形成了直接接触K⁺-NO-₃离子对,且随着溶液浓度增加,CIP物种形成需越过更大能垒。以上结果表明在KNO₃稀溶液中主要存在物种为水合K⁺和NO-₃,随浓度增大,单齿直接接触离子对(MCIP)逐渐出现。在高浓溶液或过饱和溶液中,K⁺-NO-₃离子缔合主要以单齿CIP和少量双齿CIP结构存在。     

KBr-K2SO4-H2O体系在318.15 K下的热力学性质和相平衡预测研究

本文采用电动势法对318.15 K下三元体系KBr-K₂SO₄-H₂O的热力学性质进行研究。首先,测定了KBr-H₂O溶液中KBr的电动势,线性回归出电极响应斜率κ和电极常数E⁰,结果表明实验所用离子选择性电极具有良好的能斯特响应。然后,对318.15 K下三元体系KBr-K₂SO₄-H₂O混合溶液中KBr的平均活度系数进行了研究,绘制了离子强度I及离子强度分数y_b与KBr的平均活度系数关系图,由图可得,当离子强度I一定,随着离子强度分数 y_b增大,KBr平均活度系数逐渐减小,且减小的趋势越来越大。当离子强度分数y_b是个定值时,KBr平均活度系数随着离子强度I的增大而减小。应用活度系数数据通过多元线性回归拟合出该温度条件下Pitzer模型混合离子作用参数θBr,SO₄和ψK,Br,SO₄,并计算了混合溶液中K₂SO₄的平均活度系数、渗透系数Φ,水活度a_w,超额吉布斯自由能GE。应用拟合的Pitzer混合离子相互作用参数和Pitzer模型计算了该三元体系在318.15 K下的溶解度数据,并对计算结果和其他温度下已经报道的KBr-K₂SO₄-H₂O三元体系的共饱和点处的溶解度数据进行比较,对比结果表明,溶解度计算结果可靠,拟合的离子相互作用参数具有较好的精度,可用于计算相关体系的热力学参数和相平衡的预测。     

溶液化学专刊

The present work are extract cesium (Cs_⁺) and rubidium (Rb_⁺) from the salt lake brine containing the potassium (K_⁺) and magnesium (Mg_²⁺) after concentrated through evaporation. It has excellent effect of extraction that 4-sec-butyl-2-(α-methylbenzyl) phenol (t-BAMBP) was diluted in the Sulfonated Kerosene (SK). The infrared spectrum studies indicate that polymerize to form the dimer in the t-BAMBP when Cs_⁺ or Rb_⁺ were extracted. The effect of K_⁺ and Mg_²⁺, t-BAMBP concentration, the volume ratio of organic phase to aqueous phase (O/A) and the alkalinity(pH) of aqueous phase were investigated. The K_⁺ and Mg_²⁺ should be eliminated through precipitation before extraction and separation Cs_⁺ and Rb_⁺. The experimental brine was extracted of optimum conditions were using 0.8 mol/L t-BAMBP in SK, the pH exceed 13, and O/A of 1:1 for 2 min contact time under room temperature. The optimal extraction yields of Cs_⁺ and Rb_⁺ up to 100% and 85.8%, and 8.76% K_⁺ was co-extracted. Further work target to increase theSextractionSyield and selectivity ofSRb_⁺, and realize the efficient seperation of Cs_⁺ and Rb_⁺ products .     

NH4Cl水溶液的微观结构和宏观物性研究

通过拉曼光谱、同步辐射X射线散射和密度泛函理论(DFT)模拟,研究了质量分数为1.0 %-28.0 %的NH₄Cl水溶液的微观结构变化。同时在室温下测量了粘度、接触角和电导率。由拉曼光谱和密度泛函理论模拟结果可知,当溶质浓度升高至10.0 %时,在2900 cm_-1^和3100 cm_-1^{附近出现了明显的}N-H作用峰,且随着质量分数的升高,NH₄Cl水溶液中的氢键类型发生了转变。X射线散射结果表明,当NH₄Cl水溶液质量分数升高至10.0 %时,差值对分布函数G(r)在2.98 ?附近出现明显双峰,表明在该浓度下溶液中NH₄₊^-Cl_-^{接触离子对开始成为主要微观作用形式。对}NH₄Cl水溶液的宏观物性研究表明,粘度、接触角和电导率均随着NH₄Cl水溶液质量分数的增加而增大。作者推断,NH₄Cl水溶液中氢键类型的转变、O-H...N键占比增多以及逐渐增加的NH₄₊^-Cl_-^{接触离子对},是粘度和接触角随溶质浓度增加而增加的微观本质因素;电导率的增加与溶液中有效导电离子数量增加有关。     

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。     

Characteristics and source of aerosols at Shiyi Glacier,Qilian Mountains, China

Aerosol samples were collected in the Shiyi Glacier,Qilian Mountains from July 24 to August 19,2012 and analyzed for major water-soluble ionic species(F^-,Cl^-,NO₂^-,NO₃^-,SO₄^2-,Na⁺,NH₄⁺,K⁺,Mg²⁺ and Ca²⁺) by ion chromatography. SO₄^2- and NH₄⁺ were the most abundant components of all the anions and cations,with average concentrations of 94.72 and 54.26 neq/m³,respectively,accounting for 34% and 20% of the total water-soluble ions analyzed.These mean ion concentrations were generally comparable with the background conditions in remote sites of the Qilian Mountains,but were much lower than those in certain cities in China.The particles were grouped into two dominant types according to their morphology and EDX signal:Si-rich particles and Fe-rich particles.Backward air mass trajectory analysis suggested that inland cities may contribute some anthropogenic pollution to this glacier,while the arid and semi-arid regions of central Asia were the primary sources of the mineral particles.     

The spatial and temporal distribution and characteristics of inorganic ion concentrations of TSP in the Tarim Basin

Based on Total Suspended Particulates （TSP） observations of Tazhong, Tikanli, Kashi and Minfeng in 2009, combined wa- ter-soluble inorganic ion analyses, this paper studied the spatial and temporal distribution of TSP in the Tarim Basin and analyzed concentration characteristics. The results are as follows： （1） monthly average TSP concentrations shows a similar trend in Tazhong, Tikanli, Kashi and Minfeng with peak values in April-May and low values in November-December. As for the quarter average mass concentration trends, spring has the highest value, followed by summer and autumn, and winter is the lowest; （2） total annual concentration trend of water-soluble inorganic ions in TSP is as follows： Tazhong 〉 Tikanli 〉 Minfeng 〉 Kashi. SO4^2- concentra- tions are 58%, 50%, 54% and 51% of total ion concentration; Ca^2＋ concentrations are 13%, 16%, 16% and 11%; Na^＋ concentra- tions are 12%, 13%, 10% and 12% and Cl^- concentrations are 12%, 16%, 11% and 22%, respectively. Therefore, sulfate, calcium, sodium and chloride ions are the main inorganic components of TSP in the Tarim Basin; （3） the correlation coefficients of anions and cations in Tikanli, Minfeng, Kashi and Tazhong are 0.99, 0.99, 0.25 and 0.91, respectively; the average anion concentrations are 2.57, 2.12, 2.15 and 3.02 times the average cation concentrations, indicating that ions were unbalanced; （4） SO4^2-/NO3^- ratio is much larger than the ratio of coal-fired emissions SO4^2-/NO3^-, thus the impact of fixed emission sources in the four regions on the atmosphere is far greater than that of mobile emission sources.     

中国内陆干旱、半干旱区苦咸水分布特征

通过大量野外调查、水样采集和化验分析,对中国内陆干旱、半干旱区的苦咸水和高氟水分布特征进行了初步研究。采集到的地表和地下水样中,分别有51.0%和41.5%属于苦咸水;55%和59%水样氟化物含量超标,属于高氟水。研究区的苦咸水以Cl^--Na⁺和HCO₃^--Na⁺为主要离子类型,SO₄^2--Mg²⁺和SO₄^2--Ca²⁺为次要离子类型。苦咸水和高氟水主要分布在内陆河流域下游尾闾、封闭内流区低洼湖盆低地、北部准平原化干燥剥蚀低山残丘间冲积洼地、沙漠低洼湖盆和黄土高原中西部径流系数较小的河流及部分露头潜水等区域,并具有区域富集性分布特点。季节性降水、季节性河流或渠系灌溉对苦咸水的季节性或年际间变化和空间分布有较大影响。较高浓度基质含盐量、水文地质结构、气候条件和特定的水文地球化学环境是苦咸水和高氟水形成与富集分布的主要原因。     

Investigation of Chemical Composition of Atmospheric Aerosol in Ulaanbaatar During 2005–2014

Results from investigating atmospheric aerosols in Ulaanbaatar (Mongolia) 2005–2014 are presented. It is found that the largest sources of suspended particles are represented by fuel combustion and the concomitant exhaust gases, thermal power generation, industrial facilities and mineral dust transport; the main components of aerosol particles are SO ₄ ^2- , NO ₃ ^- , Cl^–, NH ₄ ⁺ , Ca²⁺ and Na⁺. It is determined that in the wintertime, as a result of an increase in fuel consumption, calm weather and orographic characteristics of topography which contribute to accumulation of contaminants in the urban atmosphere, the average sum of ions increases to 43.9–114.6 μg/m³ against 7.44–18.48 μg/m³ during a warm season. Interannual differences in aerosol composition were noted; the total ion content averaged 43.9 μg/m³ during December 2011, 114.6 μg /m³ during December 2012, 68.7 μg/m³ during December 2013, and 64.7 μg/m³ during December 2014. It was found that the concentration of the sum of ions in the aerosol during the winter period is by a factor of 6 higher than during the summer. The highest exceedance of the concentrations was observed for the alkaline earth ions Na⁺, K⁺, Ca²⁺ and Mg²⁺ (by a factor of more than 20) forming part of the ash components. There is a difference in the chemical composition of the aerosol sampled in the center of the city and on its outskirts. It is established that the aerosol composition and concentration in Ulaanbaatar during the winter period are comparable the aerosol composition in the industrial cities of China.     

Hydrochemical Characteristics and Sodification of Groundwater in the Shirin Sou, Hamedan, Western Iran

Salinity and sodicity of groundwater are the principal water quality concerns in irrigated areas of arid and semi-arid regions. The hydrochemical characteristics and sodicity of groundwater in the Shirin Sou area, western Iran were investigated in this study by chemical analyses of groundwater samples from 49 wells. Chemical analysis of the groundwater showed that the mean concentration of the cations was in the order: Na⁺ > Ca²⁺ > Mg²⁺ > K⁺, while that for anions was SO₃ ²⁻ > Cl⁻ > HCO₃ ⁻ > NO₃ ⁻. The most prevalent water type is Na–SO₄ followed by water types Na–Cl and Ca–SO₄. The chemical evolution of groundwater is primarily controlled by water–rock interactions: mainly weathering of aluminosilicates, dissolution of sulfate minerals, and cation exchange reactions. Sulfate dissolution and pyrite weathering may both contribute to the SO₄ ²⁻ load of the groundwater. High Na⁺ concentrations in groundwater participate in ion-exchange processes, resulting in the displacement of base cations into solution and raised concentrations in groundwater. The principal component analysis (PCA) performed on groundwater identified three principal components controlling variability of groundwater chemistry. Electrical conductivity, Ca²⁺, Mg²⁺, Na⁺, SO₄ ²⁻, and Cl⁻ content were associated in the same component (PC1) (salinity), most likely linked to anthropogenic activities.     

Chemical composition of saline and subsaline lakes of the northern Great Plains,western Canada

The northern Great Plains of Canada stretch from the Precambrian Shield near Winnipeg, Manitoba, westward for ∼1,700 km to the Rocky Mountains foothills. This vast region of flat to gently rolling terrain contains a very large number of salt lakes. Major ion chemical data on ∼500 of them are available. Although the average brine (salinity, 37 ppt) is a Na⁺−SO₄ ²⁻ type of water, the lakes exhibit a wide range of salinities and ionic compositions. This diversity is confirmed by Q-mode cluster analysis; it identified thirteen major water chemistry types. Most ions display distinct trends, both spatially and with increasing salinity. All dissolved components increase with increasing salinity, but at different rates. The relative proportions of Ca²⁺ and HCO₃ ⁻+CO₃ ²⁻ ions show a strong decrease with increasing brine salinity, whereas SO₄ ²⁻ ions increase with increasing salinity. The ionic proportions of Na⁺, Mg²⁺, K⁺ and Cl⁻ exhibit no significant relationship with salinity. R-mode factor analysis of the lake water chemistry, combined with selected environmental parameters, identifies groundwater composition, climate, and the elevation of the lake within the drainage system as most important in controlling brine chemistry and salinity on a regional basis. Variability in source of ions, reaction processes and products are undoubtedly key factors in helping to explain brine chemistry of an individual basin or variation from a local perspective, but these factors are generally poorly understood and not quantified on a regional basis. Palliser Triangle Global Change Project Contribution Number 3.     

盐碱荒地开垦年限对表层土壤盐分的影响

 以典型荒漠区原生盐碱荒地及开垦农田为研究对象,通过对比研究,以阐明原生盐碱荒地开垦后不同管理措施下土壤可溶盐总量的变化规律,开垦后土壤剖面中可溶盐总量的垂直分布和季节变化规律。结果表明：开垦显著降低了0～50 cm土壤的可溶性盐含量,开垦达100 a以上老耕地的可溶性盐含量（2.31 g/kg）仅为原生盐碱荒地（26.62 g/kg）的11%;长期的耕作改变了土壤可溶性盐分在土层中的分布,原生荒漠土壤盐分具有鲜明的表聚特征,0～30 cm土层的盐分含量占整个土壤剖面的79%,开垦50 a后,土壤中的盐分分布趋于均匀,各离子浓度的垂直分布不再明显;开垦使土壤中的盐分离子组成也发生了变化,Cl^-、K⁺、Na⁺离子浓度降低,而SO₄^2-、Mg²⁺、Ca²⁺离子浓度增加,耕作层土壤由SO₄^-2-Cl^-1盐土转变为Cl^-1-SO₄^-2盐土;盐碱荒地土壤可溶盐浓度伴随着降水变化具有显著的季节变化特征,而季节对开垦耕地没有显著影响。总体而言,盐碱荒地经过多年开垦利用后,土壤可溶性盐分和pH值均显著降低。     

Effect of water quality on the leaching of potassium from sandy soil

When potassium (K⁺) fertilizers are applied to soil, K⁺ is subject to displacement through the soil profile. More generally, the application of K⁺ fertilizers to sandy soils with low clay content and small buffer capacity, in which K⁺ does not interact strongly with the soil matrix, results in localized increases in K⁺ concentration in the soil solution. Losses of K⁺ depend on the concentration of calcium (Ca²⁺) as a competing ion in the leaching water and the amount of water that passes through the soil. In this study, we examined the adsorption and movement of applied K⁺ in columns of sandy soil. Glass tubes, 4.8 cm in diameter and 40 cm in length, were packed with either native soil or Ca²⁺-saturated soil. The resulting 10-cm-long column of soil had a bulk density of 1.65 g cm⁻³. Native soil was leached with distilled water and CaCl₂ solutions of various concentrations. In the Ca²⁺-saturated soil, a pulse of K⁺ was leached with CaCl₂ solutions of various concentrations or distilled water. Increasing the CaCl₂ concentration from 3 to 15 mm resulted in earlier breakthrough, a higher peak concentration of K⁺, and greater amounts of leached K⁺. The breakthrough curve for K⁺, when leached with distilled water, showed very low concentrations and was more delayed than the other treatments. In Ca²⁺-saturated soil, the amount of K⁺ leached increased as Ca²⁺ concentration increased, with up to 54% of the added pulse K⁺ being removed from 10 pore volumes (Pv) (387 mm) of 15 mm CaCl₂. The presence of Ca²⁺ in irrigation water and soil minerals able to release Ca²⁺ is important in determining the amount of K⁺ leached from soils. Large amounts of K⁺ are leached from soils in areas where crops are irrigated with water that contains significant concentrations of Ca²⁺ and other cations.     

三氟乙酸锂-15-冠醚-5体系电迁移法分离锂同位素

锂同位素(6 Li和7 Li)在核工业中有着重要作用.锂汞齐法是目前唯一实现锂同位素工业化生产的方法,然而由于汞的使用,该方法具有较大的环境风险.开发绿色高效的锂同位素分离方法对国家能源安全具有重要意义.在本论文中,制备了溶解锂盐的冠醚溶液,并以其作为阳极液,施加电场驱动锂离子向阴极液迁移;与溶有15-冠醚-5的锂盐水...