【作者】 李梦耀；

【导师】 张小燕； 李绍卿；

【作者基本信息】 西北大学 ， 化学工程， 2003， 硕士

【摘要】 综述了化学发光分析法测定铬、锰的进展，较为详细地介绍了化学发光法的分析原理及常用化学发光试剂，讨论了影响化学发光强度的因素，归纳了化学发光在分析领域中的应用。 基于Cr（Ⅵ）—8-羟基喹啉对鲁米诺—H₂O₂化学发光体系的催化作用，建立了测定Cr（Ⅵ）的新方法。选择鲁米诺5.0×10^-4mol／L、H₂O₂为0.25mol／L、8-羟基喹啉为1.0×10^-4mol／L、Cr（Ⅵ）试液pH4.0、最终化学发光反应溶液pH12，可获得最大化学发光信号。Cr（Ⅵ）浓度在3.0×10^-6—4.0×10^-5mg／mL范围与发光强度呈线性响应，回归方程为I_CL=3.6+1.68×10⁶×c（mg／mL），检测下限C_LD为3.0×10^-6mg／mL；Cr³⁺、Mn²⁺、Co²⁺、I^-、丙酸等离子、分子干扰测定，可用掩蔽剂EDTA或阳离子交换树脂去除阳离子干扰。HNO₃消化法去除I^-和丙酸的干扰。将该法应用于生物化工产品丙酸钙、动物蛋白粉等中痕量铬的测定，相对标准偏差4.3％，加标回收率105％。5次测定平均值与苯二碳酰二肼光度法相比较，相对偏差2.7％；并探讨了化学发光的机理。 基于Mn（Ⅱ）—邻菲罗啉对鲁米诺—KIO₄化学发光体系的催化作用建立了测定Mn（Ⅱ）的新方法。当鲁米诺浓度为5.0×10^-4mol／L、KIO₄浓度为2.5×10^-4mol／L、邻菲罗啉2.5×10^-4mol／L、Mn（Ⅱ）试液pH4.0时，发光信号最强，Mn（Ⅱ）浓度在2.0×10^-6—5.0×10^-5mg／mL范围与发光强度呈线性响应，线性回归方程为I_CL=0.6+1.39×10⁶×c（mg／mL），检测限为2.0×10^-6mol／L。Cr³⁺、Fe²⁺、Co²⁺、Au³⁺等离子有干扰，使用EDTA、F^-、8-羟基喹啉等为掩蔽剂可消除或降低干扰。将该法应用于生物化工产品丙酸钙、动物蛋白粉等中痕量锰的测定，加标回收率105％，10次测定RSD为4.6％。将测定的结果与原子吸收法比较，相对偏差为8.3％，结果令人满意。此外还探讨了鲁米诺—KIO₄—Mn（Ⅱ）—邻菲罗啉化学发光的反应机理。更多还原

【Abstract】 The development on determination of trace chromium and manganese by chemiluminescence reaction is reviewed, The analysis principle of chemiluminescence reaction and chemiluminescent reagent in common use is intrduced detailly. the factors which influence a chemiluminescent intensity are investigated and Application of Chemiluminescence reaction in analytical chemistry is discribed.A sensitive and selective analytical method has been developed for determination of trace chromium. The method is based on the catalysis of 8-hydroxyquinoline -Cr ( VI ) for Luminol - H2O2 reaction system. When choose luminol concentration 5- 0×10~4 mol/L, the H2O2 act as 0. 25mol/L,8-hydroxyquinoline is 1.0×10-4mol/L, pH of Cr ( VI )test solution is 4.0 and the fina liquor pH is 12 in the chemiluminescene reaction solution, the largest chemiluminescence emission intensity may be obtained. The linear range of the working curves is 3.0×10-6 - 4.0×10-5mg/mL and the linear regression equation is an ICL = 0. 6 + 1. 39×106×c (mg/mL). Adetection limit of Cr (VI) is 3.0×10~6mg/mL. Several metal ions such as Cr3+, Mn2+, Co2+, gave heavy interference on Cr ( VI ) determination. In the presence of 1. 0×10-5mol/LEDTA, Cr2+, Mn2+and Co2+gave on interference. The method was applied to determination of trace chromium ( VI ) in some biochemical products with a satisfactry results. RSD is 4. 3%. The recovery rate of standard addition is 105%. Compared with absorptionmetric analysis of sym-diphenyl carbazide, the ralative deviation is 2.7%.A mew method has been established for determination of trace manganese, which is based on the catalysis of Mn(o -phen. )32+ for luminol-KIO4 chemiluminescent reaction. Greatest chemiluminescence emission intensity would be obtained when the concentra-tion of luminol is 5. 0×10 4mol/L, KIO4 2. 5×10~4mol/L, o -phenanthroline 2. 5×10~4mol/L, pH of Mn ( II) test solution 4.0 and the final pH in KOH reaction medium 12. The linear range is obtained from 2.0×10~6to 5.0×10~5mg/mL and the linear regression equation is an ICL = 0. 6 + 1.39×106×c (mg/mL). the detection limit of Mn ( II)is 2. 0×10~6 (mg/mL). Some coexist metal ions such as Cr3+, Fe2+, Co2+and Au3+ gave interference in Mn( II) determination. Added some screening agent such as EDTA, F-or 8-hydroxyquinoline, the interference may be remove or cut down. This method was applied to determination of trace manganese in some biochemical products with a satisfactory results. The recovery rate of standard addition is 105% and the RSD is 4.6%. Compared with atomic absorption spectrophotometry (AAS), the relative deviation is 8. 3%. The reaction mechanism of Luminol - KIO4-Mn (II ) -0 - phenanthroline system was discussed.更多还原