氯化铯和氯化镧溶剂体系及四类新化合物的合成

研究了四元体系ＣｓＣｌ－ＬａＣｌ３－ＨＣｌ－Ｈ２Ｏ（２５℃、「ＨＣｌ」＝１３％（ｗｔ），２３％（ｗｔ）和ＣｓＣｌ－ＬａＣｌ３－ＨＡｃ－Ｈ２Ｏ（３０℃，「ＨＡｃ」＝４２％（ｗｔ））的平衡态的溶度数据，并给出制了相应的溶度图，共得到了ＣｓＣｌ．ＬａＣｌ３．４Ｈ２Ｏ、２ＣｓＣｌ．ＬａＣｌ３．２Ｈ２Ｏ和３ＣｓＣｌ．ＬａＣｌ３．３Ｈ２Ｏ３种化合物。对得到的新相进行了热分析，Ｘ射线粉末衍射及偏光性质的测定，依     

2,4-二甲氧基苯甲酰氯的合成

2,4-二羟基苯甲酸与硫酸二甲酯经甲基化反应得到2,4-二甲氧基苯甲酸(3);3与SOCl2发生氯化反应合成了2,4-二甲氧基苯甲酰氯(4)。较佳的氯化反应条件为:325mmol,苯70mL,AlCl3250mg,回流反应1.5h,重结晶溶剂为石油醚(90℃～120℃),总产率达74.1%。2～4的结构经1HNMR和FT-IR表征。     

Vapor pressure,speciation, and chemical activities in highly concentrated sodium borate solutions at 277 and 317°C

The system H₂O-B₂O₃-Na₂O has been studied experimentally at 277 and 317°C. The activities of water and boric acid have been determined at mole ratios Na/B from 0 to 1.5, and total dissolved solids 3 to 80 weight percent. The activity of boric acid has been fitted to within experimental error using a speciation model with eight complex species. This model is consistent with the model previously published by Mesmer et al. The electrolyte properties of the liquid are modeled using the Pitzer-Simonson model of very concentrated electrolyte solutions. The calculated values of water activity agree with experiment, and the activity of NaOH and pOH have also been calculated. The potassium borate system also was briefly studied at 317°C, and is adequately described by a model with five complex species. The potassium borate liquid is more alkaline at K/B= 1 than a sodium borate liquid at the same mole ratio, but pOH in the two systems is the same at lower mole ratios.     

丙醇-氯化钠双水相体系萃取分离铂、钯、铑、金中的铱及其吸收光谱分析研究

提出了一种丙醇－氯化钠双水相体系萃取铱的分离－吸收光谱分析方法，在HCl介质中基于铱生成三氯亚锡酸络阴离子动力学速率与铂、钯、铑、金差异使铱与铂、钯、铑、金分离，其后在KI介质中萃取铱使其与贱金属基体分离，研究了在丙醇萃取相中铱的吸收光谱分析，并应用于实际样品中铱的测定。     

电动势法测定Cu(Ⅰ)与乙炔生成配合物的热力学函数

乙炔与Cu(I)生成配合物的热力学函数文献报道鲜见,且不同作者的测定结果差异较大。本文用改进的电动势法。对在氯丁橡胶、聚氯乙烯,乙醛等工业过程有重大意义的Cu(I)与乙炔配合物进行测定,得到更合理的结果。     

(2-甲基丙烯酰氧乙基)三甲基氯化铵-丙烯酰胺反相微乳液共聚合研究

采用SPAN-OP复合乳化剂和K_2S_2O_8-Na_2SO_3氧化还原引发剂,进行(2-甲基丙烯酰氧乙基)三甲基氯化铵-丙烯酰胺的反相微乳液共聚合。测得单体的竞聚率r_(DM·MC)=1.11±0.16,r_(AM)=0.53±0.08。在单体总浓度为20—40％(wt),引发剂浓度为0.01—0.05％,乳化剂浓度为10—18％,聚合温度为299K的条件下,得到共聚反应动力学方程:R_p=k[M]~(1.07)[I]~(0.52)[E]~(0.90),文中对上述结果做了解释。     

6—磺酰氯香豆素用作发光标记物的初探

过量C6SCl与丙氨酸在pH 9.11(H_3BO_3-NaOH)缓冲体系中,40℃反应40min,经乙酸乙酯萃取分离后,点样在层析聚酰胺膜上,用甲酸+水(1+1)展开,衍生产物得到很好的分离。斑点经1 mol·L~(-1)NaOH喷雾,紫外灯预光照10 min和干燥后,荧光强度与在4～60×10~(-11)mol范围内的丙氨酸量呈良好线性关系。在滤纸基质上,以Pb(AC)_2作重原子微扰剂,标记产物还能产生较强的室温磷光发射。研究表明,C6SCl不仅能作为氨基酸等的荧光标记物,而且可望作为其室温磷光的标记物。     

Dealkylation ofpara-nitrophenyldimethyl thiophosphate in micellar and liquid-crystalline media of then-decylammonium chloride-n-decylamine-water system

The kinetics of decomposition of p-nitrophenyldimethyl thiophosphate (1) were investigated spectrophotometrically in the n-decylammonium chloride-n-decylamine-water system (DAC-DA-H₂O), in which micellar or lamellar liquid-crystalline phases are formed as a function of the concentration of components. It was shown that1 is dealkylated in both phases. An increase in the surface charge density of associates decreases the rate of dealkylation. The activation energy in the lamellar phase is significantly higher than in the micellar phase.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1042–1048, May, 1992.     

Re-Evaluation of the Activity Coefficients of Aqueous Hydrochloric Acid Solutions up to a Molality of 2.0 Using Two-Parameter Hückel and Pitzer Equations. Part I. Results at 25°C

Simple two-parameter Hückel and Pitzer equations were used for the calculation of the activity coefficients of aqueous hydrochloric acid at 25°C up to a molality of 2.0 mol-kg^–1. The data obtained by Harned and Ehlers^(12,13) from galvanic cells without liquid junction were used in the analysis and the parameters obtained were compared to those obtained from all reliable data presented in the literature for HCl at this temperature. A good agreement between the parameters was always observed. The activity coefficients obtained by the new equations were compared to those suggested by Robinson and Stokes,⁽⁸⁾ Hamer and Wu,⁽¹⁾ and Pitzer and Mayorga,⁽⁹⁾ and good agreement was also found. The data from the most important literature data sets for HCl were also predicted using the new activity coefficient equations, and the magnitude of the resulting errors was close to the precision of the measurements, the errors forming an almost random pattern for all data sets.     

Solid-phase microextraction–capillary gas chromatography combined with microwave-induced plasma atomic-emission spectrometry for selenite determination

The use of solid-phase microextraction (SPME) with gas chromatography coupled to microwave-induced plasma atomic-emission detection (GC–MIP-AED) is described for selenite [Se(IV)] speciation. Aqueous standards were derivatised with sodium tetraethyl- or tetrapropylborate and extracted by SPME. Headspace extraction of the ethyl and propyl derivatives was studied. Relevant experimental conditions were optimised, including conditions for derivatisation and extraction and those of gas chromatographic analysis. The limits of detection achieved for headspace sampling of derivatised Se(IV) were in the low ng mL^–1 range for both ethylation and propylation. When the method was applied to analysis of selenite in selenised yeast reference material results were in good agreement with the indicated values.