钛-甘露醇-邻苯三酚红-CTMAB 四元络合体系的研究及应用

在溴化十六烷基三甲基铵(CTMAB)存在下,Ti(Ⅳ)同甘露醇和邻苯三酚红在pH 3.4时形成蓝色的四元配合物,配合物的组成为n(Ti(Ⅳ))n(甘露醇)n(邻苯三酚红)n(CTMAB)=1123,配合物的最大吸收波长为630 nm,Ti在0～1.40μg/mL范围内符合比耳定律,摩尔吸光系数为3.1×105L·mol-1·cm-1.用抗坏血酸掩蔽Fe(Ⅲ),体系不需要分离可直接用于钢中微量钛的测定.     

新显色剂4-甲氧基苯基荧光酮光度测定钛的研究及应用

研究了新显色剂 4 甲氧基苯基荧光酮 (4 MOPF)在表面活性剂溴化十六烷基三甲铵(CTMAB)与钛的显色反应条件。结果表明 ,在pH 5 .0～ 5 .7的缓冲溶液中及CTMAB存在下 ,Ti(Ⅳ )与试剂形成 1∶4的有色配合物 ,最大吸收波长位于 5 6 0nm ,摩尔吸光系数为 2 .2× 10 5L·mol-1·cm-1,钛量在 0～ 1.8μg 2 5ml符合比耳定律。显色体系灵敏度高 ,稳定 ,并有较好的选择性 ,在混合掩蔽剂存在下 ,可直接测定合金钢中的钛 ,结果满意     

光度法测定保温材料中微量钛

研究了在氨性溶液中痕量Ti(Ⅳ )催化氯酸钾氧化靛红的褪色反应 ,催化程度与Ti(Ⅳ )呈线性关系。借此建立了测定痕量Ti(Ⅳ )的吸光光度法 ,其λmax=6 12nm ,检出限为 5.0× 10 - 12 g·ml- 1,Ti(Ⅳ )浓度在 0 .0～ 0 .5μg/ 50ml范围内服从比耳定律。结合伯胺N192 3萃取分离 ,可用于保温材料中微量钛的测定     

新试剂尼泊尔鸢尾异黄酮-3''''-磺酸钠与钛的显色反应

研究了新合成的水溶性显色剂尼泊尔鸢尾异黄酮-3'-磺酸钠与Ti(Ⅳ)的显色反应.在pH 6的NH4Ac-HAc缓冲液中, 显色剂与Ti(Ⅳ) 生成12的黄色络合物, 最大吸收波长为389 nm, 表观摩尔吸光系数为3.9×104 L·mol-1·cm-1 Ti(Ⅳ)的浓度在0.1～5 μg 范围内服从比尔定律, 所拟定的方法用于超导材料铌钛合金中钛的测定.     

钛(Ⅳ)-邻硝基苯基荧光酮-平平加-十二烷基硫酸钠体系测定钛的研究和应用

本文研究了在非-阴混合型表面活性剂(平平加-SDS)存在下,钛(Ⅳ)和O-NPF的显色反应,结果表明,在0.015～0.065mol/L H_2SO_4介质中络合物非常稳定,随O-NPF浓度不同络合物组成分别为1∶2和1∶4,后者的λ_(max)=542nm,ε=2.02×10~5L·mol~(-1)·cm~(-1),钛量在0～6μg/25ml范围内服从比尔定律。方法的灵敏度高,选择性好,用于合金钢样和有机钛中钛的直接测定,结果满意。     

新试剂尼泊尔鸢尾异黄酮-3′-磺酸钠与钛的显色反应

研究了新合成的水溶性显色剂尼泊尔鸢尾异黄酮-3′-磺酸钠与Ti(Ⅳ)的显色反应。在pH 6的NH4Ac-HAc缓冲液中,显色剂与Ti(Ⅳ)生成1∶2的黄色络合物,最大吸收波长为389 nm,表观摩尔吸光系数为3.9×104L.mol-1.cm-1Ti(Ⅳ)的浓度在0.1~5μg范围内服从比尔定律,所拟定的方法用于超导材料铌钛合金中钛的测定。     

磷钼钛酸-耐尔蓝-聚乙烯醇体系光度法测定痕量钛

在0.9～1.3mol/L高氯酸介质中,Ti(Ⅳ)、P(Ⅴ)与钼酸铵反应形成磷钼钛杂多酸,在聚乙烯醇(PVA)存在下,杂多酸与耐尔蓝(NB)形成离子缔合物。离子缔合物的最大吸收位于590nm,表观摩尔吸光系数为1.94×10~5L·mol~(-1)·Cm~(-1),服从比耳定律范围0～4.8μgTi/25ml。主要组成摩尔比为Ti:P:NB:1:3:3。至少稳定5h。此法用于某些钢样和铝合金中钛的测定,结果满意。     

钛(Ⅳ)同邻苯二酚紫的四元混配型胶溶络合物的形成及其分光光度研究

在溴化十六烷基三甲基铵(CTMAB)的存在下,钛(Ⅳ)同羟胺和邻苯二酚紫(PV)于pH3时形成绿色的四元混配型胶溶络合物,其组成比为:Ti(IV):NH_2OH:PV:CTMAB=1:2:2:4。λ_(max)=730nm,反应对比度△λ=290nm,摩尔吸光系数ε_(730)=9.4×10~4。方法可直接用于某些钢铁和合金中微量钛的测定。     

铝合金中钛的光度分析法研究

提出过渡金属钛与新显色剂对溴偶氮羧 M的高灵敏显色反应。考查了介质的酸度、温度、有机溶剂和表面活性剂对 β型配合物形成的影响。在pH 2 .6～ 3.6时 ,显色剂与钛在室温下形成稳定的β型配合物。表观摩尔吸光系数ε715=1.2× 10 5L·mol- 1·cm- 1,钛含量在 0～ 16μg/2 5ml范围内服从比耳定律 ,配合物的组成比为Ti∶R =1∶2。用于铝合金中钛的测定 ,结果满意     

流动注射分光光度法测定钢铁及铝合金中微量钛

钢铁中微量钛的测定多采用二安替吡啉甲烷吸光光度法,方法较成熟,但灵敏度较低,测量时间也较长。本文基于在稀硫酸和溴化十六烷基三甲基铵介质中,Ti(Ⅳ)与邻氯苯基荧光酮生成有色络合物的性质,建立了测定Ti(Ⅳ)的流动注射分光光度法。该方法的测定范围为0.1～1.5μg·ml~(-1),进样频率为120样·h~(-1)。本法用于钢铁及铝合金中微量钛的测定。取得了满意的结果。     

SPECTRAL CHARACTERISTICS OF THE EXCITED STATES OF THE PRODUCT OF THE CHEMILUMINESCENCE OF LUMINOL*

Abstract— In dimethylsulfoxide the emission spectrum of luminol chemiluminescence is red-shifted by 300 cm^-1 from the photoexcited fluorescence of the product 3-aminophthalate dianion, while in aqueous solvent the two spectra are identical. The spectral properties of the product dianion have been measured in aqueous solvent and in a number of aprotic solvents, both at room temperature and at 77°K. The ground states and the excited states from which emissions are observed are characterized. Two alternatives are presented to explain the aprotic emission spectra.     

丙烯聚合络合催化剂形成过程的研究

以倍半物为还原剂还原TiCl_4,经异戊醚络合处理,然后在TiCl_4己烷溶液中35℃条件下热处理,制得对丙烯聚合具有高活性和高定向度的络合催化剂。研究了制备过程中各步反应产物的组成和结构特征,并讨论了TiCl_3低温晶型转变机理。     

光谱透射比标准物质的研究

研制了紫外、可见、近红外光谱区通用光谱透射比较标准物质。以高纯熔融石英为基片材料，镍铬合金的镀膜材料，采用双光楔对称光胶结构以消除同色杂散光的影响，对镀膜进行光胶处理以保证膜层的强度、稳定性及光学中性，采用高精度分光光度测量装置作为定值手段的以保证准确的定值，设计定位保护架以消除多次反射误差。该光度标准适用的光谱范围的200-2600nm，光谱透射比定值不确定度为0.5%。     

六氟丙烯等离子体聚合机理研究

<正> 在以前的工作中,我们曾应用色谱-质谱(GC-MS)及顺磁共振(ESR)等方法研究了四氟乙烯和三氟氯乙烯等离子体聚合过程中气体冷凝物的组成及结构,提出自由基引发聚合反应机理。本文用类似方法研究六氟丙烯(HFP)等离子体气体冷凝物的组成与结构和冷凝物的ESR信号及其从低温到高温的变化规律,证实了自由基的稳定性并提出气相聚合反应机理。     

ON THE ACCURACY OF DIFFERENTIAL MEASUREMENTS OF THE MINIMAL ERYTHEMA DOSE: INFLUENCE OF THE DISCRETENESS OF THE SCALE

The minimal erythema dose (MED) is often used as a quantity by which the influence of certain treatments of the skin can be measured. Differential measurements are performed by assessing the difference of the MED on the skin treated in some way and the untreated skin.
As the MED-measuring scale is discrete, the question is sometimes raised whether it is possible to measure differences smaller than one scale unit. In the present paper it is shown that this is indeed possible; in principle the discreteness of the scale does not impose any restriction on the smallest value of the difference that can be measured. The discreteness of the scale introduces an extra random variation into the measurement. This variation is estimated theoretically. It is automatically included in the usual error analysis.
The discreteness variance is small when compared to other variance components, which are computed from an analysis of variance of actual experiments. Reducing the discreteness variance, by reducing the dose decrement of the MED-measuring scale, therefore, does not enhance the overall accuracy considerably. Finally, it is found that the assessments of the MED by the various observers do not differ significantly from each other, and that multiple assessments do increase the accuracy, especially for small effects.     

THE MOLECULAR WEIGHT DEPENDENCE OF THE SPREADING FACTOR OF SEC COLUMNS AND THE SURFACE STRUCTURE OF THE PORE OF PACKINGS

The molecular weight separation and column dispersion for a number of SEC columns packedwith various packing materials were calibrated simultaneously using narrow MWD polystyrene stan-dards as probe. The molecular weight dependence of the spreading factor is closely related to thesurface structure in the pore of packings.     

聚三氟氯乙烯热解产物的鉴识

本文报道了聚三氟氯乙烯减压热解产物中,沸点较低部分的一些氟氯烃类的分离和鉴识。已经鉴识的有氟氯烷类五个,单烯类六个,双烯及环单烯各一个,并对各种产物的生成机制进行了讨论。     

THE KINETICS OF THE DECOMPOSITION OF CYCLOHEXYL HYDROPEROXIDE IN THE PRESENCE OF VANADYL DIBENZOYLMETHANE

The kinetics of the decomposition of cyclohexyl hydroperoxide(CHHP) in benzene catalyzed by vanadyl dibenzoylmethane[V0(DBM).,] has been studied.It was found that the products of decomposition of CHHP were cyclohexanol and cyclohexanone,which are produced in about equimolar amount,and the product cyclohexanol obviously inhibited the decomposition of CHHP.The kinetics data can be satisfactorily described by the following equation (with [CHHP]0>>[VO(DBM)2]0)R0=kK[CHHP]0[VO(DBM)2]0/(1+k[CHHP]0)This is the kinetic evidence for the formation of a catalyst-hydro-peroxide intermediate.In the equation K is the stability constant of the catalyst-hydroperoxide intermediate complex;k is the rate constant for the decomposition of the complex.The rate constant K at 500℃ may be expressed as follows:k=1.9×108exp(-53.7×103/RT)S-1 with the activation energy Ea=53.7kJ mol-1     

稳盐对扁平卤化银微晶增感中心大小和分布的影响

5-甲基-7-羟基-1,3,4三氮吲哚嗪(简称稳盐TAI)作为乳剂制备过程的有机稳定剂,已得到广泛应用.一些作者发现,稳盐除了作为稳定剂之外,对部分乳剂还有增感作用.Tani^[1]在硫敏化的立方体溴化银乳剂中加入稳盐,发现可使乳剂的感光度成倍增加,而稳盐对扁平颗粒和八面体颗粒的溴化银乳剂的增感效果较小.