273 K下Na2CO3-Na2SO4-Na2B4O7-H2O四元体系介稳相平衡的实验研究

采用等温蒸发法研究了四元体系Na2CO3-Na2SO4-Na2B4O7-H2O在273 K时的介稳相平衡及平衡液相的密度. 利用溶解度数据绘制了该四元体系273 K下的相图. 研究结果表明, 该四元体系有异成分复盐2Na2SO4·Na2CO3形成. 相图中有2个共饱点、5条单变量曲线和4个结晶相区. 4个结晶相区分别为盐Na2CO3·10H2O, Na2SO4·10H2O, Na2B4O7·10H2O和2Na2SO4·Na2CO3的结晶区. 复盐2Na2SO4·Na2CO3同时存在于包含Na2CO3-Na2SO4-H2O三元体系的其它四元体系或高元体系中. 在273 K介稳平衡相图中, 碳酸钠以Na2CO3·10H2O形式析出; 硫酸钠以Na2SO4·10H2O的形式析出; 硼酸钠的完整分子式为Na2B4O5(OH)4·8H2O. Na2CO3对Na2B4O7有盐析作用.     

Na+, K+//Cl-, B4O2-7-H2O四元体系273 K介稳相平衡

采用等温蒸发法研究了四元体系Na+, K+//Cl-, B4O2-7-H2O 273 K时的介稳相平衡与相图. 测定了该体系273 K平衡液相中各组分的溶解度及平衡液相的密度; 绘制了该体系的介稳相图. 该四元体系273 K相图由5条溶解度单变量线、4个结晶区及2个共饱和点组成. 体系无复盐或固溶体形成. 四个结晶区分别对应单盐NaCl、KCl、K2B4O7·4H2O 和Na2B4O7·10H2O. 共饱点E1处KCl、NaCl及Na2B4O7·10H2O三盐共饱和,所对应的平衡液相组成为w(Cl-)=29.15%, w(B4O2-7)=0.64%, w(K+)=5.97%, w(Na+)=15.55%; 共饱和点E2处盐KCl、Na2B4O7·10H2O和K2B4O7·4H2O的三盐共饱和, 所对应的平衡液相组成为w(Cl-)=22.84%, w(B4O2-7)=10.98%, w(K+)=28.01%, w(Na+)=1.53%. 同体系298 K时的稳定相图相比, 273 K时硼酸钠的结晶区变大, 而硼酸钾、氯化钠结晶区变小.     

298.16K时Na~ ,Mg~(2 )//Cl~-,SO_4~(2-),NO_3~-,H_2O体系中NaCl饱和区域相平衡

采用等温溶解平衡法研究了五元体系Na ,Mg2 //Cl-,SO42-,NO3-,H2O在298.16K下氯化钠饱和平衡体系的溶解度,获得了相应的投影干盐图、氯图和水图.研究结果表明,在298·16K下氯化钠饱和时,该五元体系投影干盐图由8个二盐共饱和的双变面、13条三盐共饱的单变线和6个四盐共饱的零变点构成,存在两种复盐,8个二盐共饱双变面分别对应于NaCl NaNO3,NaCl Na2SO4,NaCl MgCl2·6H2O,NaCl MgSO4·Na2SO4·4H2O,NaCl Mg(NO3)2·6H2O,NaCl NaNO3·Na2SO4·2H2O,NaCl MgSO4·7H2O和NaCl MgSO4·(1~6)H2O.讨论了该相图在新疆硝酸盐矿开发利用过程中的应用.     

298.16 K时Na+, Mg2+//Cl-, SO42-, NO3-, H2O体系中NaCl饱和区域相平衡

采用等温溶解平衡法研究了五元体系Na+, Mg2+//Cl-, SO42-, NO3-, H2O在298.16 K下氯化钠饱和平衡体系的溶解度, 获得了相应的投影干盐图、氯图和水图. 研究结果表明, 在298.16 K下氯化钠饱和时, 该五元体系投影干盐图由8个二盐共饱和的双变面、13条三盐共饱的单变线和6个四盐共饱的零变点构成, 存在两种复盐, 8个二盐共饱双变面分别对应于NaCl+NaNO3, NaCl+Na2SO4, NaCl+MgCl2·6H2O, NaCl+MgSO4·Na2SO4·4H2O, NaCl+Mg(NO3)2·6H2O, NaCl+NaNO3·Na2SO4·2H2O, NaCl+MgSO4·7H2O 和NaCl+MgSO4·(1—6)H2O. 讨论了该相图在新疆硝酸盐矿开发利用过程中的应用.     

硫酸镁亚型盐湖卤水高温蒸发析盐结晶规律（英文）

针对青海大浪滩盐湖区硫酸镁亚型盐田卤水进行了高温蒸发结晶规律的研究,结果表明该盐田卤水在102~122℃高温蒸发时析盐顺序为:MgSO4·H2O、NaCl、MgSO4·6H2O、KCl·MgCl2·6H2O和其他混盐.通过对不同温度下的液相组分分析和固相X射线衍射分析表明,利用高温蒸发开采此种卤水时,最适宜的蒸发温度应控制在117℃左右.此时,该卤水组成中SO2-4的质量分数低于2%,同时K+还未析出,可以简化为Na+,K+,Mg2+//Cl-—H2O四元体系,以便达到开采氯化钾的工艺需求,为该盐湖卤水的综合开发利用提供理论参考.     

四元交互体系Cd2+, Na+//Cl-, SO42——H2O 298 K时的相平衡

采用等温溶解平衡法研究了四元交互体系Cd2+, Na+//Cl-, SO2-4-H2O在298 K的相平衡关系. 研究发现, 该平衡体系存在Na2CdCl4·3H2O复盐相区, 平衡相图中有七条单变度曲线, 三个共饱和点和五个结晶相区. 其平衡固相的结晶区分别为Na2SO4、CdSO4、CdCl2·2.5H2O、Na2CdCl4·3H2O和NaCl. 该四元交互体系平衡液相的物化性质随着Cd2+浓度的增加呈现有规律的变化. 研究结果表明, 镉盐在该体系中的溶解度大, 迁移性强, 增加了土壤环境污染风险.     

Na^+, K^+//Cl^-, SO4^2^-, CO3^2^——H2O五元体系25℃介稳相图的研究

用等温蒸发方法研究了NaCl饱和下的Na^+, K^+//Cl^-, SO4^2^-, CO3^2^--H2O五元体系25℃介稳相图, 测定了溶液的密度、粘度、折光率、电导率、PH和蒸汽压, 并由蒸汽压数据求得了水活度和渗透系数。在Janecke相图上有五个结晶区, 即Na2SO4,Na2CO3·2Na2SO3, Na2SO4·3K2SO4, Na2CO3·7H2O和KCl相区, 与Harvie和Weare计算相图比较, 无水芒硝和七水碳酸钠结晶区明显扩大, 碳钠矾相区明显缩小, 钾石盐和钾芒硝相区基本相近。用经验或半经验公式描述了溶液的密度、折光率和粘度随浓度的变化规律。用Pitzer电解质溶液模型计算了水活度和析出盐的溶度积。结果是令人满意的。     

Na^+, K^+//Cl^-, SO4^2^-, CO3^2^——H2O五元体系25℃介稳相图的研究

用等温蒸发方法研究了NaCl饱和下的Na^+, K^+//Cl^-, SO4^2^-, CO3^2^--H2O五元体系25℃介稳相图, 测定了溶液的密度、粘度、折光率、电导率、PH和蒸汽压, 并由蒸汽压数据求得了水活度和渗透系数。在Janecke相图上有五个结晶区, 即Na2SO4,Na2CO3·2Na2SO3, Na2SO4·3K2SO4, Na2CO3·7H2O和KCl相区, 与Harvie和Weare计算相图比较, 无水芒硝和七水碳酸钠结晶区明显扩大, 碳钠矾相区明显缩小, 钾石盐和钾芒硝相区基本相近。用经验或半经验公式描述了溶液的密度、折光率和粘度随浓度的变化规律。用Pitzer电解质溶液模型计算了水活度和析出盐的溶度积。结果是令人满意的。     

Na2B4O7-Na2SO4-NaCl-H2O四元体系288K相平衡研究

采用等温溶解平衡法研究了四元体系Na2B4O7-Na2SO4-NaCl-H2O在288 K的相平衡关系,测定了平衡液相的溶解度及其密度。由研究结果知该四元体系为简单共饱和型,无复盐及固溶体形成。根据实验数据绘制了相应的相图。相图中有一个共饱点,三条单变曲线,三个结晶区平衡固相分别为:Na2B4O7·10H2O,Na2SO4·10H2O和NaCl。实验结果表明NaCl对Na2B4O7和Na2SO4有盐析作用,并简要讨论了实验结果。     

Na+, K+, Mg2+∥Cl-, SO2-4-H2O五元体系35 ℃介稳相图研究

研究得出（Na+, K+, Mg2+∥Cl-, SO2-4-H2O）五元体系35 ℃时的介稳溶解度数据,绘制了该体系35 ℃的介稳相图,共有9个为氯化钠所饱和的结晶区域：氯化钾、钾芒硝（3K2SO4*Na2SO4）、钾镁矾（K2SO4*MgSO4*4H2O）、钾盐镁矾（KCl*MgSO4*2.75H2O）、光卤石（KCl*MgCl2*6H2O）、白钠镁矾（Na2SO4*MgSO4*4H2O）、硫酸钠、六水硫酸镁（MgSO4*6H2O）和水氯镁石（MgCl2*6H2O）. 所得35 ℃介稳相图与Vant Hoff 25 ℃稳定相图比较有较大区别：软钾镁矾（K2SO4*MgSO4*6H2O）、七水硫酸镁、五水硫酸镁及四水硫酸镁结晶区域消失,钾镁矾和钾盐镁矾结晶区域显著扩大. 所得35 ℃介稳相图与25 ℃介稳相图区别很大：软钾镁矾和七水硫酸镁结晶区域消失,同时出现了钾镁矾和钾盐镁矾的结晶区域. 在该五元体系35 ℃介稳相平衡研究中发现析出的是钾盐镁矾的低水化合物（KCl*MgSO4*2.75H2O）.     

三门峡虢季墓遗址盐害分析与调查

针对三门峡虢季墓遗址部分区域存在起甲、泛白、疱疹等由可溶盐引起的病害,在其遗址不同部位取样进行土遗址本体含盐分析.取样区域包括虢季墓、梁姬墓和近代墓遗址.采用X射线荧光光谱(XRF)和离子色谱(IC)分析所取样品的可溶盐成分、含量及可溶盐成盐元素在土遗址中的成盐规律.采用电子能谱(XPS)和X射线衍射(XRD)分析样品的物相组成及盐分状态,扫描电子显微镜/能谱(SEM/EDS)进一步考察含盐土质的颗粒组成、微观形貌等.结果表明:虢季墓取样区域所含盐分主要为Na_2SO_4、CaCO_3和少量的其他盐分如CaCl_2、KNO_3和NaCl等.靠近地面部位所取样品盐分含量高于其他部位,盐害表现更为明显.梁姬墓取样区域总盐分含量略高于虢季墓与近代墓,硝酸盐含量较高.而近代墓遗址可溶盐盐分含量略低,盐害不明显.在不同取样点可溶盐含量有所差异,但在邻近区域,其成盐具有一定规律性,这一点对于遗址基体中盐害的深入研究与防治具有重要意义.     

Effects of inorganic ions on the binding of triflupromazine and chlorpromazine to bovine serum albumin studied by spectrometric methods

The effects of inorganic salts, NaCl, NaBr, NaI, Na2SO4, KCl, KBr, KI, on the binding constants (Ks) of psychotropic phenothiazine drugs, triflupromazine (TFZ) and chlorpromazine, to bovine serum albumin (BSA) were examined by using second-derivative spectrophotometry. All of the salts examined, with the exception of Na2SO4, decreased the K values significantly, depending on the concentration of the salt, e.g., the decrease in the K values of both drugs were about 40% for 0.1 M NaCl. The results obtained with Na2SO4 indicated that neither Na+ nor SO4(2-) had any affect on the binding of the phenothiazines to BSA. Based on the Na2SO4 results and the finding that the effect of each potassium salt on binding was quite similar to that of the corresponding sodium salt, the effects of these halogen salts can be considered to be derived from their anions, although the phenothiazines are positively charged at pH 7.4. The effectiveness of the anions was determined to occur in the following order: I->Br->Cl-; these results coincided with the published order of the binding affinity of these anions to albumin. The 19F-NMR spectra of TFZ in the presence of each of these halogen salts revealed a concentration-dependent decrease in the intensity of the signal at 13.8 ppm that had previously been assigned to the TFZ bound to Site II. Consequently, the effects of these anions on the binding of positively charged phenothiazine drugs are thought to be local steric effects caused by the binding of these anions to Site II.     

Thermal studies on the sodium salts of aminosalicylic acids

The effect on the stability of the isomers of aminosalicylic acid of formation of their sodium salts has been studied by use of differential scanning calorimetry and thermogravimetry, coupled with evolved gas analysis by Fourier transform infrared spectroscopy. X-ray powder diffraction and infrared spectroscopy provided complementary information. The DSC curves for the sodium salts of all of the isomers showed complex dehydration/decomposition endotherms. From the initial mass losses of the TG curves, the amounts of water per mole of salt were estimated as 0.5, 2.4 and 1.4 moles for the sodium salts of 3-aminosalicylic acid, 4-aminosalicylic acid and 5-aminosalicylic acid, respectively. TG-FTIR results for the sodium salt of 3-aminosalicylic acid showed the evolution of carbon dioxide in three stages: below 150°C, between 200 and 300°C and continuous formation up to 500°C. This behaviour differs from that of 3-aminosalicylic acid itself, which forms CO₂ between 225 and 290°C. For the sodium salt of 4-aminosalicylic acid, the formation of carbon dioxide starts from 250°C and is still being formed at about 650°C. 4-aminosalicylic acid decarboxylates above 150°C. 5-aminosalicylic acid and its sodium salt showed no evolution of carbon dioxide below 600°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Novel cation [N(SO2NMe3)2]+ and its synthesis and crystal structure. Dichloride of imido-bis(sulfuric) acid HN(SO2Cl)2. Part 1. Crystal structures of KN(SO2Cl)2.(1/2)CH3CN, KN(SO2Cl)2.(1/6)CH2Cl2, and [PCl4][N(SO2Cl)2

Several salts of bis(chlorosulfonyl)imide HN(SO2Cl)2 (1), namely, two solvates of its potassium salt, KN(SO2Cl)2.(1/2)CH3CN (1K1), KN(SO2Cl)2.(1/6)CH2Cl2 (1K2), and its tetrachlorophosphonium salt, [PCl4][N(SO2Cl)2] (2), were prepared and structurally characterized. The reaction of HN(SO2Cl)2 with Me3N gives the [N(SO2Cl)2]- salt of a novel cation, [N(SO2NMe3)2]+. This cation is analogous to the [HC(SO2NMe3)2]+ cation, but in contrast to the latter, it is fairly stable to hydrolysis. The salt [N(SO2NMe3)2]+[N(SO2Cl)2]- (3) can be converted into salts of other anions by being treated with diluted aqueous solutions of the respective acids, and thus NO3-, Cl-.H2O, SeO3(2-), CH3COO-, HSO4-, (COO)2(2-) salts were prepared. Treatment of 3 with concentrated HNO3 gave the [N(SO2NMe3)2]+ [O2NO-H-ONO2]- salt, and the addition of an HCl-acidified FeCl3 aqueous solution yielded the FeCl4- salt. Methanolysis resulted in the formation of MeOSO3- and [MeOSO2NSO2OMe]- salts. All salts have been characterized by chemical analysis, vibrational spectroscopy, and X-ray structure determinations.     

胆酸盐在酸性介质中自聚集作用的共振瑞利散射光谱及其分析应用研究

研究了牛磺胆酸钠、甘牛胆酸钠、胆酸钠和脱氧胆酸钠等四种胆酸盐在酸性介质中的聚集作用对共振瑞利散射光谱的影响及其分析应用. 结果表明: 在一定浓度的HCl, H₂SO₄或HNO₃溶液中, 四种胆酸盐均能自聚集形成粒径增大的聚集体. 该聚集体能导致溶液RRS显著增强, 并产生了新的RRS光谱. 不同胆酸盐在同种介质中的反应产物具有相似的光谱特征, 最大RRS波长分别位于349 (HNO₃介质), 359 (H₂SO₄介质)和369 nm (HCl介质). 在一定范围内, 胆酸盐的浓度与散射强度(ΔI_RRS)成正比. 对于不同的体系其检出限在12.0～21.8 ng/mL之间. 方法灵敏度高, 选择性较好, 而且十分简便快速. 可用于市售蛇胆川贝液和血清样品中胆酸盐的测定.     

Improved matrix-assisted laser desorption/ionization mass spectrometric detection of glycosaminoglycan disaccharides as cesium salts

Ultraviolet matrix-assisted laser desorption/ionization mass spectrometric (UV-MALDI-MS) analysis of highly acidic, thermally labile species such as glycosaminoglycan-derived oligosaccharides is complicated by their poor ionization efficiency and tendency to fragment through the loss of sulfo groups. We have utilized a systematic approach to evaluate the effect of alkali metal counterions on the degree of fragmentation through SO3 loss from a highly sulfated model compound, sucrose octasulfate (SOS). The lithium, sodium, potassium, rubidium, and cesium salts of SOS were analyzed by UV-MALDI-time-of-flight (TOF)MS using an ionic liquid matrix, bis-1,1,3,3-tetramethylguanidinium alpha-cyano-4-hydroxycinnamate. The positive-ion and negative-ion MALDI mass spectra of five alkali metal salts of SOS were compared in terms of the degree of analyte fragmentation through the SO3 loss and the absolute intensity of a molecular ion signal. Experimental results demonstrate that the lithium, sodium, and potassium salts of SOS undergo some degree of fragmentation through the loss of SO3, whereas the fragmentation through the loss of SO3 in the rubidium and cesium salts of SOS is suppressed. A high detection sensitivity associated with the stability of sulfate half-esters was achieved for the cesium salt of SOS using positive-ion detection. Finally, the cesium salt of chondroitin sulfate A disaccharide was successfully analyzed using UV-MALDI-TOFMS.     

外加盐作用形成的正负离子表面活性剂双水相

癸基三乙基溴化铵-癸基磺酸钠（C10NE-C10SO3）等摩尔混合均相体系（即使在表面活性剂总浓度高达0.2 mol•L－1时仍然可形成稳定的均相溶液）在外加盐NaF、Na2SO4和Na3PO4的作用下可自发分离成两个水相（双水相）.研究了该类双水相体系的形成、相行为及其对牛血清蛋白（BSA）的分配，并与普通的正负离子表面活性剂混合双水相体系进行了比较.结果表明，该类双水相体系克服了普通的正负离子表面活性剂混合双水相体系的一些不足，具有一些独特的优点.该类双水相体系的相行为可以通过外加盐进行调控,通过外加盐的种类来调控和优化BSA的分配行为.图1表2参8     

Studies on the Effects of Salt and Surfactant in Wet Phase Separation of Polysulfone

This study investigates the effect of additives in the nonsolvent water in terms of cloud point during the phase inversion of Polysulfone (PS) in dimethyl formamide (DMF). The exponential pattern is observed with PS concentration (0.2 to 0.6% (w/w)). It needs a low amount of water to get the cloud point at low temperature. The cloud point varied with the nature of water matrix and depended on the amount of salt, as well as the PS amount. The presence of salts (sodium chloride and sodium sulfate) lowers the cloud point of the solution. The network distribution of the particles at the cloud point is disturbed in the presence of salt. The requirement is more for Sodium lauryl sulfate (SLS) added water to reach the cloud point in the low range of PS solution up to 0.3% PS (w/w). The morphological and distribution pattern of PS particles are very different compared to PS particles produced from pure water. XRD study of PS particles produced from the mixed water system reflects relatively more amorphous character with respect to PS particles from pure water. The presence of both surfactant and salts in water systems also influences the cloud point in synergistic manner.     

离子色谱法分析保险粉工业回收甲酸钠中的阴离子

 利用单柱阴离子交换色谱法测定了保险粉工业回收产品中的甲酸,Cl－,SO,NO,羟乙基硫代硫酸盐,SO和S2O。以1．8mmol／L邻苯二甲酸和1．35mmol／L三羟甲基氨基甲烷的混合溶液作淋洗液,流速为1．0mL／min时,分离效果良好。7种离子的加标回收率在96％～102％之间,检测下限在0．2～5mg／L之间,方法准确、简便。     

Hydrogenation of 4-(2-furyl)-2-oxobutenoic acid sodium salt on Raney nickel

The hydrogenation of 4-(2-furyl)-2-oxobutenoic acid sodium salt on a nickel catalyst has been studied. Using Raney nickel catalyst, the corresponding salts of 4-(2-furyl)-2-oxobutanoic acid, 4-(2-furtyl)-2-hydroxybutanoic acid, and aliphatic hydrogenolysis products of the initial compound were obtained. The sodium salt of 2-hydroxy-4-(2-tetrahydrofuryl) butanoic acid and the condensation product 4-(2-furylethyl)-3-(2-furylmethyl)-2-oxo-3,4-didehydroglutaric acid were detected in the hydrogenolysate. A method has been developed for obtaining the sodium salts of 4-(2-furyl)-2-oxobutanoic and 4-(2-furyl)-2-hydroxybutanoic acids.Latvian Institute of Organic Synthesis, Riga LV-1006, e-mail: elmira@osi.lanet.lv. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 41–45, January, 1998.