示波催化极谱法测定高纯铅中痕量硒

在氨水-氯化铵-亚硫酸钠-高碘酸钾混合底液中,硒产生灵敏的催化极谱波,测定起始电位为-0.64V,峰电位为-0.84V(υs.SCE),一阶导数法测定,硒含量在0～5.0μg·L-1范围内与峰电流呈线性,检出限为0.1μg·L-1。以硫酸铅沉淀分离主体铅,可测定高纯铅中wse2×10-5%×10-4,方法灵敏。试验了高纯铅中20余种共存离子的干扰,方法具有很好的选择性,其他共存杂质元素均不干扰。用于高纯铅中痕量硒测定,加标回收率为96%～99%,RSD为9.1%～11%,测定结果与二氨基联苯胺光度法一致,方法简便、灵敏、准确。     

硒-高碘酸钾催化极谱法测定痕量的硒

本文提出了硒-高碘酸钾催化极谱法测定痕量硒的适宜底液,给出了简单、快速而准确地测定0.000X—0.00000X％硒的分析方法。对硒-高碘酸钾催化波的机理作了初步探讨,指出此催化波的性质可能是由于SeSO_3~2-吸附在汞滴表面上改变了滴汞电极的性质,使IO_4~-提前还原而产生了很大的催化电流。     

紫外吸光光度法测定化妆品中木瓜蛋白酶的活力

样品用磷酸盐 半胱氨酸 ＥＤＴＡ缓冲溶液搅拌溶解后 ,选择一定的 ｐＨ值和温度条件 ,样品中的木瓜蛋白酶能将加入的酪蛋白水解生成可溶解的氨基酸 ,末水解的酪蛋白用三氯乙酸沉淀后过滤 ,溶解的水解产物用紫外吸光光度法测定[1] 。1　试验部分1.1　试剂与仪器磷酸钠溶液 :0 .0 5ｍｏｌ·Ｌ- 1,称取十二水磷酸氢二钠 1.79ｇ溶解于 10 0ｍｌ水中。柠檬酸溶液 :0 .0 5ｍｏｌ·Ｌ- 1,将柠檬酸一水合物1.0 5ｇ用 10 0ｍｌ水溶解。缓冲溶液 :称取十二水磷酸氢二钠 17.89ｇ溶于80 0ｍｌ水中 ,再将ＥＤＴＡ钠盐二水合物 14.0 ｇ和盐酸半胱氨酸一…     

SeSO_3~(2-)-IO_3~-催化波机理的研究

由于SeSO_3~(2-)在含亚硫酸钠的氨性高碘酸钾底液中能产生灵敏度高、选择性好、抗干扰性强的催化波,有时勿需分离就可直接测定多种试样中0.00x—0.000x%硒,若结合某些分离手段,还可以测定复杂试样中0.0000x—0.00000x%硒,因而得到广泛应用。但是,关于催化波机理的研究还不够深入。作者在实践中发现,用碘酸钾代替高碘酸钾,得到与上述文献相同的效果。本文对SeSO_3~(2-)-IO_3~-催化波的机理进行了研究,表明SeSO_3~(2-)-IO_3~-与SeSO_3~(2-)-IO_4~-催化波的机理完全一致,从而认为该催化波不是平行催化波或SeSO_3~(2-)吸附在汞滴表面上改变了     

催化动力学法测定人发中痕量硒

催化动力学褪色法测定痕量硒已有报道[1 ,2 ] ,但大都存在Ｆｅ3+、Ｃｕ2 +等共存离子的干扰。在实际分析中常需对样品进行繁琐的预处理。实验研究了在盐酸溶液中 ,以ＥＤＴＡ作掩蔽剂 ,痕量硒催化氯酸钾氧化 5 Ｂｒ ＰＡＤＡＰ褪色反应及其动力学条件 ,以加硒催化反应与不加硒非催化反应的吸光度之差△Ａ对温度 1 /Ｔ作图得一直线 ,由Ａｒｒｈｅｎｉｕｓ式求得该反应的活化能Ｅａ=94ｋＪ/ｍｏｌ,建立了测定硒的新方法。方法检测限为 5.7× 1 0 - 5μｇ/ｍｌ,Ｓｅ(Ⅳ)的测定范围为 0～ 0 .4μｇ/ 2 5ｍｌ,用此法测定人发中痕量硒 ,结果令人满…     

碲的新极谱催化波及催化极谱法连续测定矿物岩石中的碲和硒

碲和硒在矿物岩石中含量甚微,一般同时要求测定这两元素。极谱测定法虽有报导,但或是灵敏度不足,或是不能在同一底液中连续测定硒、碲。本文发现在氨性酒石酸溶液中引入适量Pb-EDTA时,于-0.8伏处出现一敏锐的碲极谱催化波,具有很高的灵敏度,检测限为5×10~(-4)μg ml~(-1)。在-0.5伏处硒亦有一清晰的极谱波可与碲同时测定。若加入高碘     

偶氮胭脂红B动力学光度法测定Fe(III)

动力学光度法测定铁[1,2]多用2,4 二氯苯酚+4 氨基安替比林[3]、苄橙[4]、次甲基蓝[5]、酸性铬蓝Ｋ[6]和二溴对甲基偶氮羧[7]等为监测组分,以Ｈ2Ｏ2为氧化剂,α,α 联吡啶为活化剂。本文用催化光度法确定铁(ＩＩＩ)催化高碘酸钾氧化偶氮胭脂红Ｂ褪色反应的动力学条件及有关参数,仅以高碘酸钾为氧化剂,不使用活化剂,操作简单、快速,用于水样及生物样中铁的测定,结果满意。1　实验部分移取0 20ｍｌＦｅ(ＩＩＩ)标准工作溶液(1 0μｇ/ｍｌ)于25ｍｌ比色管中,依次加入2 0ｍｌ0 02ｍｏｌ/Ｌ硫酸溶液,1 5ｍｌ0 010ｍｏｌ/Ｌ高碘酸钾溶液,1 5ｍ…     

动力学光度法测定食品中的碘

催化动力学光度法测定痕量碘 ,大多使用Ｃｅ(ＩＶ) -Ａｓ(ＩＩＩ)体系[1 3] 。我们的实验发现在硫酸介质中 ,Ｉ- 能强烈催化高碘酸钾氧化苋菜红的褪色反应 ,在波长 5 2 5ｎｍ处 ,其反应速度与碘离子的浓度之间符合动力学一级反应关系式 ,并且此法灵敏度、选择性均较高。1　实验部分取两支 2 5ｍｌ比色管 ,各加入 2 0ｍｌ浓度为8 0× 1 0 - 3ｍｏｌ/Ｌ苋菜红溶液 ,3 5ｍｌ( 1 0ｍｏｌ/Ｌ)Ｈ2 ＳＯ4,2 0ｍｌＫＩＯ4( 0 2 0ｍｏｌ/Ｌ)溶液。向其中一支加入适量碘标准溶液 ( 1 μｇ/ｍｌ) (吸光度为Ａ) ,另一支不加碘 (吸光度为Ａ0 ) ,用水…     

关于配位滴定测定水的总硬度终点返红问题的讨论

ＥＤＴＡ滴定法测定水的总硬度时 ,常以 0 .1ｍｏｌ·Ｌ-1氨 氯化铵缓冲液调节溶液ｐＨ为 1 0 ,以络黑Ｔ为指示剂 ,用 0 .0 1ｍｏｌ·Ｌ-1ＥＤＴＡ滴定。此方法使用过程中经常出现终点返红问题。本文对此进行了试验。1　试验部分1 .1　主要仪器与试剂ＣＯ2 发生器 (自制 )氨 氯化铵缓冲溶液 :0 .1ｍｏｌ·Ｌ-1所用试剂均为分析纯以上1 .2　试验方法取自来水样 1 0 0 .0ｍｌ,以 0 .1ｍｏｌ·Ｌ-1氨 氯化铵缓冲液调节其 ｐＨ为 1 0 ,加络黑Ｔ指示剂 (与ＮａＣｌ配比为 1∶1 0 0 )少许 ,以 0 .0 1 0 0 0ｍｏｌ·Ｌ-1ＥＤＴＡ标准溶液滴定至终点…     

微分脉冲极谱法测定水中痕量的Se(Ⅳ)和Se(Ⅵ)

本文使用悬汞电极微分脉冲极谱法于硒(Ⅳ)-亚硫酸钠-高氯酸-氨水-酒石酸铵-碘酸钾体系的极谱催化波测定水中痕量的硒(Ⅳ)和硒(Ⅵ).选择了最佳测定条件,试验了Te~(4+)、Hg~(2+)、腐植酸等十三种物质的影响程度,检出限0.01μg/1。硒浓度在0～1.0μg/1的范围内与峰电流成线性关系,相对标准偏差10-14％,回收率为95-100％。     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。