忽略第二级离解的判据推导和二元弱酸溶液氢离子浓度的近似计算*

为推导出忽略二元弱酸$H_{2}A$第二级离解的判据,设计了虚拟酸A和虚拟酸B并计算了酒石酸、虚拟酸A和虚拟酸B的准确氢离子浓度$[H^{+}]_{T}$和近似氢离子浓度$[H^{+}]_{AV}$。计算结果表明:忽略$H_{2}A$第二级离解的判据与$\frac{K_{a1}}{K_{a2}}$比值相关。从极端二元酸($K_{a1}=K_{a2}$)得到的判据为$\frac{2K_{a2}}{[H^{+}]_{AV}}为推导出忽略二元弱酸H_2A第二级离解的判据,设计了虚拟酸A和虚拟酸B并计算了酒石酸、虚拟酸A和虚拟酸B的准确氢离子浓度[H~+]_T和近似氢离子浓度[H~+]_(AV)。计算结果表明:忽略H_2A第二级离解的判据与■比值相关。从极端二元酸(K_(a1)=K_(a2))得到的判据为■,其中[H~+]_(AV)=■。■≤0.11判据具有广泛的普适性,可以用于所有二元弱酸溶液。新判据除了保证溶液氢离子浓度近似值[H~+]_(AV)的准确度外(误差SymbolqB@5%以内),同时还具有覆盖浓度区间宽的显著优点。     

甲烷在Ni/TiO2催化剂表面的活化

考察了Ni/TiO2催化剂甲烷部分氧化和二氧化碳重整制合成气的反应活性,实验表明,以TiO2为载体的镍系催化剂对于甲烷部分氧化制合成气反应具有较好的活性,尤其对H2的选择性较高,对二氧化碳重整制合成气反应具有较好的低温反应活性.采用脉冲-质谱在线分析等技术,在无气相氧条件下向Ni/TiO2催化剂脉冲CH4,发现甲烷在催化剂表面的活化（转化）及其氧化产物的选择性与金属催化剂表面氧的浓度密切相关.CH4与Ni/TiO2催化剂作用过程中存在明显的氢溢流和氧溢流现象,可能是这种溢流效应使得Ni/TiO2催化剂具有良好的反应活性和抗积碳性能.     

分光光度法测定萃余液中氯仿浓度

用NaOH-吡啶比色法可以测定水或某些废水中的微量CHCl3浓度,但测定N,N-二甲基甲酰胺(DMF)废水经CHCl3萃取DMF后的萃余液中CHCl3浓度时,DMF对显色的有严重的干扰。采用蒸馏预处理后,再用比色法测定蒸馏所得的馏液中CHCl3浓度的方法,可以消除废水中DMF对显色的干扰。研究了水样中DMF浓度、蒸馏汽化率等因素对比色时显色的影响,建立了蒸馏-比色法测定DMF废水萃余液中微量或大量CHCl3浓度的分析方法。对含10g/LDMF水样的测定,CHCl3的线性范围为0～0.75g/L;与顶空色谱法测定结果对比,测定CHCl3浓度为5g/L和0.16g/L水样的相对误差分别为2.1%和1.2%;对CHCl3浓度为0.575g/L的水样进行7次平行测定,相对标准偏差为6.6%。对含DMF<15g/L水样的分析,结果令人满意。     

Coupled membrane process applied to fruit juice concentration

A coupled membrane process of membrane distillation and osmotic evaporation, where the solutions were thermostated separately at different temperatures, was developed. Enhanced water flux was obtained since the total driving force of the coupled process was higher than the sum of the driving forces of single processes. Apple, raspberry, sour cherry, red, and black currant juices were concentrated by the novel, mild technique. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

Distribution of Impurities During Low-Temperature Directed Crystallization of Water Solutions

Trends in the distribution of impurities at low-temperature directed crystallization of water solutions of various concentrations are described and the mechanism of their incorporation in the solid phase is explained. The data on the distribution coefficients of the impurities between the solid and liquid phases are presented. It is shown that the behavior of the impurities in the process of directed crystallization is the same and does not depend on the nature of the macrocomponent. The unique case of CsI is explained due to the negative values of hydration of iodide and cesium ions. It is recommended to use the observed trends for the purification of water or analytical pre-concentration of impurities.The coefficients of enrichment of the impurities after low-temperature directed crystallization of aqueous solutions with different composition and total concentration of the dissolved salts are estimated and their dependencies on the composition and concentration of the aqueous solution are shown.     

双十八烷基二甲基氯化铵水溶液CMC值的测定

采用电导法和荧光法测定了阳离子表面活性剂-双十八烷基二甲基氯化铵(DODAC)的临界胶束浓度(CMC), 在温度为14 ℃时, 电导法测得DODAC溶液的临界胶束浓度为5.24×10-5 mol/L, 荧光法测得DODAC溶液的临界胶束浓度为9.67×10-5 mol/L.     

浆态床反应器中相含率及粒径分布的研究

以空气－水－石英砂体系为对象，研究了费托合成浆态床反应器中表观气速、平均淤浆浓度、床层轴向位置等因素对气含率、固体浓度轴向分布和粒径分布的影响，并通过实验得出了气含率与操作变量之间的关联式。     

烷基咪唑离子液体对脂肪酶催化酯水解反应活性的影响

考察了1-烷基-3-甲基咪唑类离子液体对柱状假丝酵母脂肪酶(CRL)催化橄榄油水解反应活性的影响,利用电导法确定了磷酸盐缓冲液中Br^-,Cl^-,[BF₄]^-系列咪唑离子液体的临界胶束浓度(CMC)和[PF₆]^-系列咪唑离子液体的溶解度.结果显示,离子液体的阴、阳离子对酶活性的影响规律与离子液体的Kosmotropicity性质无明显关联,但与离子液体在体系中的含量密切相关,在最适离子液体含量时,酶活性达到最高;阳离子[C_nMIM]⁺中的n越大,可促进酶活性的离子液体适宜含量越低;Br^-,[BF₄]^-系列离子液体的浓度超过CMC时则抑制酶活;阴离子对酶活性的最大促进作用顺序为Br^->Cl^->[BF₄]^->[PF₆]^-.离子液体对酶活性的影响随体系pH和温度的不同而改变,在最适离子液体浓度时的最适pH均为7.000.在pH 7.000,30 ^oC以及[C₈MIM]Br离子液体浓度为47.6 mmol/L的最佳条件下,最高相对酶活力和比活力分别达到1734%和54.4 U/mg protein.     

大核树枝状大分子的合成及其凝血、溶血性能研究

从 8 0年代中期开始 ,Ｔｏｍａｌｉａ、Ｎｅｗｋｏｍｅ、Ｆｒｅｃｈｅｔ等对树枝状大分子开展了卓有成效的研究 ,合成了多种结构的树枝状大分子[1 ] ,并对它们的应用进行了积极的探讨 .在数枝状大分子的合成方面 ,寻找新的多官能团引发核就是一个研究热点 ,例如采用大分子核 ,Ｆｒｅｃｈｅｔ等采用聚乙二醇作为核用收敛法合成了聚芳醚和聚芳酯树枝状大分子[2 ,3] ,为嵌段共聚增添了新的内容 .而Ｔｏｍａｌｉａ等以氨和乙二胺等小分子为核合成的聚酰胺 胺类树枝状大分子呈粘糊状[4] ,取样、称量等操作很麻烦 ,其应用也受到限制 .聚乙二醇无毒…     

Determination of total fluorine in blood at trace concentration levels by the Wickbold decomposition method with direct potentiometric detection

The Wickbold decomposition method in combination with differential potentiometric detection via fluoride ion-selective electrode has been applied to analysis of total fluorine in biological matrices. The performance of the method has been evaluated for determination of total fluorine in rat blood. Total mineralization of the biological sample is achieved by combustion of the sample in oxygen/hydrogen flame and subsequent absorption of the resulting fluoride in aqueous absorption medium. The fluoride is then quantified by highly selective automated differential static potentiometry with fluoride ion-selective electrode. Total fluorine determination has been evaluated in terms of sample carryover, reproducibility, precision, as well as feasibility to routine analysis of alternative biological matrices. Our results indicate that, up to 100 ppm fluorine in blood, the method does not suffer from sample carryover. Limits of quantitation of 0.5 ppm and limits of detection of 0.24 ppm fluorine in 0.5 g blood samples were achieved by elimination of inherent limitations of fluoride ion-selective electrode detection via automated differential static potentiometric measurements. The Wickbold decomposition method was found to be suitable for routine total fluorine determination in blood samples despite its relatively low throughput and high operator skill requirements.