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对比Na BH4碱性溶液Cu、Ag、Ni、Pt和Au电极的循环伏安特性发现,BH-4在Au电极上活性最强,Pt有一定的活性,而Cu、Ag及Ni几乎没有活性。用三电极体系研究了BH-4在Au电极上的氧化机理,分析了碱性体系中不同浓度Na BH4溶液的线性循环伏安特性,讨论了扫描速度、OH-和B(OH)-4浓度等对BH-4氧化峰电位及峰电流的影响。结果表明,以Au电极为工作电极的峰值电流法是BH-4离子定性和定量检测的一种简单、快速、准确的方法。同时,溶液中较大浓度范围内变化的OH-和B(OH)-4对Na BH4的分析无明显影响。 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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采用三电极体系,以Ag/AgCl为参比电极,Ti片为辅助电极,用伏安法和电化学阻抗谱(EIS)研究了酸性溶液中Mn2+在玻碳电极表面的氧化机理,讨论了扫描速度、温度、酸度等对Mn2+氧化电位及电流的影响。结果表明,常温下控制Mn2+和H2SO4浓度,阳极反应为Mn2+→Mn OOH。当温度升高时,由于阳极大量释放O2,进而发生4Mn OOH+O2→4Mn O2+2H2O反应。因此,通常Mn2+在H2SO4溶液中升温电解的主要阳极反应为,Mn2+→Mn4+→Mn(OH)4,当温度升高至70℃以上时有Mn3+生成,但Mn3+不稳定发生歧化反应生成Mn2+和Mn O2。 相似文献
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库仑法和电化学阻抗法是测量锂离子扩散系数有效的测量手段。以实验室自制的LiFePO4为实验电池正极材料,介绍如何用库仑法和阻抗法测试并计算电极材料的锂离子扩散系数。库仑法计算得到锂离子扩散系数由Li1-xFePO4(x=0)的9.6×10-9cm2.s-1变化为Li1-xFePO4(x=0.7)的1.1×10-11cm2.s-1。用阻抗法的两种模型,分别计算了Li1-xFePO4(x=0.65)的电池材料的锂离子扩散系数,结果分别是8.5×10-11cm2.s-1和3.1×10-12cm2.s-1。三种方法的计算结果接近。 相似文献
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提出用氯离子选择电极测定艾比湖水体中氯离子含量的方法,并研究了测定条件。标准曲线在1.0×10-1～1.0×10-4mol/L范围内呈良好的线性关系,回收率为95.6%～103%,RSD为1.51%～4.34%,结果表明该方法简便、快速、准确。 相似文献
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以4-硝基苯并-15-冠醚-5(4-NO_2-B15C5)做萃取剂,苯甲醚和1-丁基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐([C_4mim][NTf_2])作稀释剂和协萃剂,以1 mol/L LiCl溶液作萃取溶剂,构建高效的冠醚—离子液体/锂盐溶液的溶剂萃取体系。重点考察了有机相组成、冠醚浓度和锂盐阴离子等对锂同位素分离的影响。结果表明,4-硝基苯并-15-冠醚-5具有良好的锂同位素分离效果,在萃取CF_3COOLi时最大单级分离系数(α)可达1.043±0.01。 相似文献
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用等压法研究了LiCl-Li2 B4O7-H2 O体系离子强度范围为 0 1 5 3 0～ 3 0 75 8mol kg-1不同质量摩尔浓度分数的等压平衡浓度 ,水活度 ;计算了LiCl和Li2 B4O7,混合盐溶液的饱和蒸汽压 ,渗透系数等热力学性质。以总硼浓度 0 0 8mol·kg-1为界 ,把所有混合盐的实验数据分为高浓度和低浓度两部分 ,按照不同的物种生成转化反应 ,考虑溶液中H3 BO3 和硼氧配阴离子B(OH) 4 -,B3 O3 (OH) 4 -和B4O5(OH) 4 2 -的存在形式。由实验数据用最小二乘法和迭代法求取了LiB(OH) 4 离子对的缔合平衡常数Km1,B3 O3 ,(OH) 4 离子的生成转化反应的化学计量平衡常数Km2 ,以及Pitzer模型的离子相互作用参数。用该模型计算的渗透系数值与实验结果取得合理的一致。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 相似文献
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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(CF3SO2)2与否对[C6MIm]+离子电迁移的影响。总的来说,随着电流的增加,[C6MIm]+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(CF3SO2)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,[C6MIm]+离子的迁移量明显减少。在电极溶液中溶入LiN(CF3SO2)2时或者将LiN(CF3SO2)2溶入离子液体时,[C6MIm]+离子的迁移量也明显受到抑制。 相似文献
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采用重量法对2014年、2015年、2017年采暖期乌鲁木齐市新疆农业大学大气颗粒物TSP、PM10、PM2.5进行采集，使用TAS-990型火焰原子吸收分光光度计、PF3型原子荧光光谱仪、石墨炉原子吸收分光光度计测定颗粒物中5种重金属元素的质量浓度，利用富集因子法分析重金属元素的富集程度及来源。结果表明：该采样点采暖期大气颗粒物TSP、PM10的质量浓度在近几年均呈现出下降趋势，PM2.5的质量浓度变化趋势为：2017年＞2015年＞2014年；重金属元素As的质量浓度在不同粒径大气颗粒物中均为最高值，且采暖期大气颗粒物中除Cr以外的重金属含量、重金属元素的富集程度近几年均呈现明显的下降趋势；重金属As、Cr、Zn、Hg元素更易富集于细颗粒物中。 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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Heavy metals,one of the most toxic classes of pollutants,are resistant to degradation and harmful to the biological environment.The lakes that have developed on the Tibetan Plateau are ideal regions to investigate historic heavy metal pollution,particularly through the use of the reliable 210 Pb dating technique.Environmental magnetism has been successfully applied to estimate heavy metal pollution in different environmental systems due to its characteristics of simple processing steps,good sensitivity,and non-destructibility.However,it has not yet been applied to assess heavy metal pollution in lake sediments on the Tibetan Plateau.A series of environmental magnetic investigations of Qiangyong Co Lake sediments(southern Tibetan Plateau) was therefore conducted to explore the relationship between magnetic minerals and mercury(Hg) concentrations.The results showed that the magnetic mineral species in lake sediments remained stable,with similar levels of four different components from 1899 to 2011.However,the proportion of component 1(C1,hematite) increased continuously with the corresponding decrease in the proportion of C2(goethite),while the proportions of C3 and C4(magnetite) did not change significantly.As a result,the bulk magnetic signals(e.g.,SIRM and clf) were unsuitable for the evaluation of the Hg concentration;however,the proportion of hematite had a strong positive correlation with the Hg concentration.It is possible that the Qiangyong Glacier(the main water supply for Qiangyong Co Lake) has experienced faster melting with global and local warming,and the Hg trapped in cryoconite and ice was released.Hematite,with a large specific surface area,has a strong capacity for absorbing Hg,and both materials are ultimately transported to Qiangyong Co Lake.The proportion of hematite in a sample is therefore a suitable semi-quantitative proxy that can be used to evaluate the Hg concentration in Qiangyong Co Lake sediments.This study confirmed that the variation of magnetic minerals can provide a new method to estimate the variation of Hg concentrations and to study the process of Hg deposition in lakes in the southern Tibetan Plateau on the basis of a detailed environmental magnetic analysis. 相似文献
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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. 相似文献
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黄河下游滩区开封段土壤重金属空间分异规律 总被引：5，自引：0，他引：5
对黄河下游滩区开封段及滩外土壤采样48个,按照土壤化学分析方法,对铅(Pb)、铬(Cr)、汞(Hg)、砷(As)和镉(Cd)5种重金属进行分析,采用单因子污染指数、普通克里格法和相关分析对研究区土壤重金属含量特征、污染状况和分布特征进行了计算。结果表明:①研究区土壤5种重金属Pb、Cr、Hg、As和Cd含量就平均值而言,Cr的平均含量最大,Pb、Hg的平均含量最小。Pb、Cr、Hg、As和Cd4种重金属元素的变异系数在0.13～0.28之间,属于中等变异强度,Hg变异系数较大,Hg的空间差异相对较大;②重金属元素Pb、Cr、Hg、As、Cd之间具有较强的线性关系,可能具有共同来源——水沙输入;③主要污染元素为Hg、As、Pb,其中Pb的污染为中度污染且范围较广,而As和汞Hg构成三级轻度污染。Cr和Cd在各村间变化不大,Cr,Cd没有构成污染,且Cd是全部清洁表现出污染没有积累;④土壤各重金属元素的空间分布特征在研究区内上下段之间分异明显,上段呈清洁状态,中段有少量污染,下段表现出明显富集的分布状态。 相似文献
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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E0,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yb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 yb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yb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θBr,SO4和ψK,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aw,超额吉布斯自由能GE。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。 相似文献