Kinetics and Mechanism of Iridium(Ⅲ)-Catalyzed Oxidation of Ethanol Amine by Cerium(Ⅳ) in Sulfuric Acid Media

In this study, the kinetics and mechanism of the iridium（ Ⅲ ） -catalyzed oxidation of ethanol amine（EAN） by cerium（Ⅳ） in a sulfuric acid medium was investigated using titrimetric technique of redox in a temperature range of 298--313 K. It was found that the reaction is of first order with respect to Ce（ Ⅳ ） and It（ Ⅲ ）, and a positive fractional order with respect to EAN. It was also found that the pseudo-first-order （ [EAN ] 〉〉 [ Ce （ Ⅳ） ] ） rate constant koba decreases with the increase of [ H^＋ ] and [ HSO^-4 ]. Under the protection of nitrogen gas, the reaction system can initiate the polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a suitable mechanism was proposed. From the dependence of koba on the concentration of hydrogen sulfate, Ce（SO4）2 was found to be the kinetically active species. The rate constants of the rote-determining step together with the activation parameters were evaluated.

Chemiluminescence Determination of Tetracycline and Oxytetracycline in Pharmaceutical Preparations Using Ru(bipy)_3^(2+)-Cerium(Ⅳ) System

A new chemiluminescence (CL) method for the determination of tetracycline and oxytetracycline is developed, hased on the CL reaction of tetracycline and oxytetracycline with Ru(bipy)_3~2+ and Ce(IV). In sulfuric acid medium, the CL emission is generated upon continuous oxidation of Ru(bipy)_3~2+ by cerium (IV ). The emission intensity is greatly enhanced when tetracycline and oxytetracycline are introduced into the reaction system after acid degradation. Under the optimum conditions, the calibration curves are linear over the range of 8. 0 X 10^-8^-4. 0 X 10^-6 mol/L for tetracycline and of 2. 0 X 10^-7~4. 0 X 10^-5 mol/L for oxytetracycline, with the detection limits are 4. 2 X 10^-8 mol/L for tetracycline and 1. 5 X 10^-7 mol/L for oxytetracycline, respectively. The proposed method was used for the determination of tetracycline and oxytetracycline in pharmaceutical formulations with good results.

硫酸铈(Ⅳ)对镍沉积层晶粒细化和电结晶行为的影响

在工业电沉积镍的过程中,镍的晶粒尺寸将会直接影响其在工业生产中的使用情况。因此,细化沉积层晶粒就显得尤为重要。本文选用三电极体系,通过测试工业电解液中不同(0~1.5 g/L)硫酸铈(Ⅳ)浓度下阴极极化曲线、循环伏安曲线和计时电流曲线,探究硫酸铈(Ⅳ)对电沉积镍电结晶行为的影响规律;通过扫描电镜和X射线衍射对哈林槽实验获得的镍沉积层的晶粒尺寸和结构取向进行分析,探究硫酸铈(Ⅳ)对工业电解中镍沉积层晶粒细化及晶体生长取向的影响。结果表明:添加硫酸铈(Ⅳ)后,镍的起始沉积电位发生负移,阴极过电位增大,硫酸铈(Ⅳ)的加入对镍的电结晶起促进作用。未加入硫酸铈(Ⅳ)时,沉积层晶粒粗大不均匀;随着添加剂的加入,使镍沉积层晶粒明显细化;当硫酸铈(Ⅳ)的浓度为0.6 g/L时,峰值电流最大且形核弛豫时间最短,沉积层晶粒尺寸最小,细化效果最优,因此,0.6 g/L硫酸铈(Ⅳ)为硫酸铈(Ⅳ)的最优添加浓度。

A study of phosphate adsorption by different temperature treated hydrous cerium oxides

An alkaline precipitation method was introduced to produce hydrous cerium oxides.The prepared powder was characterized by Brunauer-Emmett-Teller（BET） nitrogen adsorption-desorption,X-ray diffraction（XRD）,Fourier transform infrared（FTIR） spectrometry,and thermal gravimetry（TG） approaches.The adsorbent has a chemical formula of CeO2·nH2O（n 2） and a cubic fluorite-type structure after high temperature treatment.Adsorption capacity of different temperature treated hydrous cerium oxides does not directly correlate with BET specific surface area.Phosphate adsorption isotherms follow the Langmuir equation below the treatment temperature of 800°C.Phosphate adsorption causes no change on the structure of a hydrous cerium oxides,and no signs of CePO4 precipitates are found.The ion-exchanging structure of hydrous cerium oxide plays a fundamental role in phosphate adsorption.The structure is highly temperature resistant and forms adsorption sites which adsorb both water and some anions.Complete loss of adsorption ability cannot be achieved unless the treatment temperature is higher than 1200°C.Mechanism study shows that the adsorption of phosphates is mainly an anion-exchange process.

Adsorption of Ce(Ⅳ) Anionic Nitrato Complexes onto Anion Exchangers and Its Application for Ce(Ⅳ) Separation from Rare Earths(Ⅲ)

Ce （Ⅳ） nitrato complexes were adsorbed on two anion exchangers based on polyvinyl pyridine （PVP） and quatemized PVP incorporated into porous silica matrix. The effect of nitric acid concentration （0.5～6 mol·L^-1） and temperature （278 ～318 K） on Ce（ Ⅳ ） sorption efficiency was investigated. Sorption increased with increasing nitric acid concentration, indicating that [Ce（NO3）6]^2- complex is the main adsorbed Ce（Ⅳ） species. Oxidation of sorbents by adsorbed Ce （ Ⅳ ） species resulting in Ce （ Ⅲ ） release to the solution was observed. Pyridine based anion exchangers exhibited higher oxidation stability compared to the commercial strong base anion exchanger. Ce（ Ⅳ ） reduction was temperature dependent and obeyed pseudo-first-order reaction kinetics. Column separation of Ce （ Ⅳ ） from La （ Ⅲ ） and Y （ Ⅲ ） was carried out from 6 mol·L^-1 nitric acid with PVP based anion exchanger. Reasonable Ce （Ⅳ） breakthrough capacity （0.7 mol·kg^-1 PVP） was achieved. No remarkable decrease of capacity was observed within 3 consequent runs. In contrast, Ce （Ⅲ） leakage due to reduction decreased and breakthrough capacity slightly increased. This effect was more pronounced with increasing temperature. Regeneration with 0.1 mol·L^- 1 nitric acid was successful （recovery 100% ± 4% ） and Ce solution of high purity （ 〉 99.97% ） with respect to La and Y content was gained.

Color-Fading Spectrophotometric Determination of Cerium with DBC-Arsenazo

In the medium of 0.18～1.08 mol·L^(-1) sulfuric acid, cerium(Ⅳ) has the color-fading effect on DBC-arsenazo. The apparent molar absorptivity of the color-fading reaction is ε _(530 nm)=1.03×10~4 L·mol^(-1)·cm^(-1). Beer′s law is obeyed over the range of 1.20～12.0 μg·ml^(-1) of Ce (Ⅳ) which shows a linear relationship with the decrease in the absorbance of the colored solution. The effect of thirty-six coexisting ions was studied. The method was applied to the determination of the trace amount of cerium in water samples and has the advantage of high accuracy and good selectivity.

EFFECT OF CERIUM ION IMPLANTATION ON THE AQUEOUS CORROSION BEHAVIOR OF ZIRCONIUM

In order to study the influence of cerium ion implantation on the aqueous corrosion behavior of zirconium, specimens were implanted by cerium ions with a dosage range from 1×1016 to 1×1017 ions/cm2 at about 150℃, using MEVVA source at an acceler ative voltage of 40kV. The valence of the surface layer was analyzed by X-ray photo- electron spectroscopy (XPS); Three-sweep potentiodynamic polarization measurement was employed to value the aqueous corrosion resistance of zirconium in a 0.5mol/L H2SO4 solution. It was found that a remarkable decline in the aqueous corrosion behavior of zirconium implanted with cerium ions compared with that of the as-received zirconium. Finally, the mechanism of the corrosion resistance decline of the cerium-implanted zirconium is discussed.

Effect of cerium ion on the proliferation,differentiation and mineralization function of primary mouse osteoblasts in vitro

The effects of cerium ion(Ce3+) on the proliferation,differentiation,adipocytic transdifferentiation and mineralization function of primary mouse osteoblasts(OBs) were investigated.The results indicated that Ce3+ at all concentrations(1×10-9,1×10-8,1×10-7,1×10-6,1×10-5,and 1×10-4 mol/L) promoted the proliferation of osteoblasts(OBs).On day 1 and 3,Ce3+ promoted the differentiation of OBs at concentrations of 1×10-9,1×10-7,and 1×10-6 mol/L,but inhibited the differentiation of OBs at higher concentrations.On ...

Study on Solubility of Cerium(Ⅳ) Phosphate

The solubility product constant of cerium(Ⅳ) phosphate according to the concentration of phosphate detected by spectrophotometer at pH=0.4 and 20 ℃ were determined. The solubility product constant of cerium(Ⅳ) phosphate is 2.915×10 -34. The reliability of determination data is proved by s=0.004 and CV=1.30%. The result indicate that solubility product constant of cerium(Ⅳ) phosphate is effected by temperature and acidity significantly. Therefore, temperature and acidity increase over a particular range could result in an increase of solubility of cerium(Ⅳ) phosphate.

Mechanism of Cerium Ions Scavenging Superoxide Radical

The mechanism of cerium ions scavenging superoxide radical(O÷2) has been studied. The results show that (1) Ce^3+ can reduce O÷2 to H_2O_2 while it is oxidized to Ce^4+; (2) Ce^4+ can oxidize O÷2 to O_2 while it is reduced to Ce^3+.

Accurate electron affinity of atomic cerium and excited states of its anion

Electron affinities(EA)of most lanthanide elements still remain unknown owing to their relatively lower EA values and the fairly complicated electronic structures.In the present work,we report the high-resolution photoelectron spectra of atomic cerium anion Ce−using the slow electron velocity-map imaging method in combination with a cold ion trap.The electron affinity of Ce is determined to be 4840.62(21)cm^-1 or 0.600160(26)eV.Moreover,several excited states of Ce(^4H9/2,^4I9/2,^2H9/2,^2G9/2,^2G7/2,^4H13/2,^2F5/2,and ^4I13/2)are observed.

铬(Ⅲ)离子催化铈(Ⅳ)离子氧化异丁醇的反应动力学及机理

在酸性介质中用氧化还原滴定法研究了铈(Ⅳ)离子在铬(Ⅲ)离子催化作用下,于25～40℃区间氧化异丁醇的化学反应动力学.结果表明反应对铈(Ⅳ)离子为一级,对异丁醇的表观反应级数为正分数.准一级速率常数kobs随催化剂[Cr(Ⅲ)]增加而增大,亦随[H+]增加而增大,但随[HSO4-]增加而减小.在氮气保护下,反应不能引发丙烯酰胺聚合,说明在反应中没有自由基产生.提出了催化剂、底物和氧化剂间生成双核加合物的反应机理,通过kobs与HSO4-的依赖关系,找到本反应体系的动力学活性物种是Ce(SO4)2+,并计算出平衡常数、速控步骤的速率常数及相应的活化参数.

云南沱茶自水溶液中对铈(Ⅳ)离子的富集作用

研究了云南沱茶在不同浓度、温度、pH条件下,自水溶液中吸附Ce(Ⅳ)离子的特性,并分别讨论了阴离子表面活性剂十二烷基硫酸钠(SDS),阳离子表面活性剂氯代十六烷基吡啶(CPC)和非离子表面活性剂聚乙二醇辛基苯基醚(OP)对沱茶吸附Ce(Ⅳ)离子的影响,结果表明,在一定条件下,沱茶对铈(Ⅳ)的吸附量可达7.95mg·g-1,吸附规律符合Langmuir等温方程,计算了吸附热,对沱茶吸附Ce(Ⅳ)离子的机理进行了讨论。

岩藻聚糖硫酸酯寡糖-Ce(Ⅳ)配合物水解胶原蛋白的研究

对岩藻聚糖硫酸酯寡糖．铈配合物的制备及其对胶原蛋白的水解活性进行了研究。通过酸水解得到不同分子量的岩藻聚糖硫酸酯寡糖F1（MW〉5ooo），F2（MW1000-500），F3（MW〈1000），小分子的F3与Ce（Ⅳ）的配合效果最好，且水解胶原蛋白的活性高。通过实验确定了岩藻聚糖硫酸酯寡糖F3与Ce（Ⅳ）的配合条件以及F3-Ce（Ⅳ）配合物对胶原蛋白的最佳水解条件。

GC—MS／SIM法同时测定食品中的苏丹红Ⅰ～Ⅳ

采用气相色谱-质谱(GC-MS)选择离子检测法(SIM),建立了准确可靠、灵敏度高、快速简便的同时测定食品中苏丹红Ⅰ～Ⅳ的新方法.色谱柱为PR-SR石英毛细管柱(20 m×0.25 mm),进样口温度280℃,柱温200℃,以15℃/min升至280℃;柱前压130 kPa,载气He;EI离子源,选择m/z 77,105,115,143,176,247,248,261,352,380用于SIM检测,并按不同的采样时间分成4组,每组4个离子,分别对应于每种苏丹红进行定性分析确证;选择苏丹红Ⅰ～Ⅳ各自的分子离子峰m/z 248,276,352,380作抽出离子图进行定量分析.苏丹红Ⅰ、Ⅱ的线性范围为0.01～10.0 mg/L,苏丹红Ⅲ、Ⅳ的线性范围为0.1～10.0 mg/L;检出限苏丹红Ⅰ、Ⅱ为1μg/kg,苏丹红Ⅲ为5μg/kg,苏丹红Ⅳ为10μg/kg;回收率86%～95%.本法与欧洲健康与消费者保护委员会的方法(HPLC法)相比灵敏度高1～2个数量级,分析时间缩短,用色谱保留时间、质谱同时定性,消除了食品中杂质的干扰,结果准确可靠,选择性和重复性好,适用于所有食品成品及原料的检验.

铈Ⅳ与抗坏血酸的荧光反应及其分析应用

实验发现,抗坏血酸在水溶液中能将无荧光的铈(Ⅳ)离子还原成能发射特征荧光的铈离子,加入三磷酸钠,可使体系的荧光强度大大增强,由此建立了间接灵敏测定抗坏血酸的方法.用1 cm石英比色池在激发和发射波长分别为303 nm和353 nm处测定其荧光强度;抗坏血酸在1.0×10-7～6.0×10-6 mol/L浓度范围内与体系的荧光强度呈线性关系;相关系数为0.9989; 检出限为1.0×10-8 mol/L(S/N=3).该法应用于样品测定,结果令人满意.

用流动注射法研究巯基化合物-铈(Ⅳ)-氢化可的松的化学发光反应

采用流动注射法研究了巯基化合物－铈（Ⅳ）－氢化可的松（ＨＣＲｓ）体系的化学发光行 为，对影响化学发光强度的诸因素进行试验和探讨，建立了流动注射化学发光法检测谷胱甘 肽（ＧＳＨ），半胱氨酸（Ｃｙｓ）等含巯基化合物的新方法。检测ＧＳＨ和Ｃｙｓ和线性范围分别为 ２．０×１０－６～１０．０×１０－５ｍｏｌ／Ｌ和１．０×１０－６ｍｏｌ／Ｌ～１０．０×１０－５ｍｏｌ／Ｌ；检测限分别为２．０ ×１０－７ｍｏｌ／Ｌ和１．４×１０－６ｍｏｌ／Ｌ（Ｓ／Ｎ＝３）；ＧＳＨ、Ｃｙｓ加入血清中进行回收测定的回收率 为９０％～９５％，相对标准偏差小于４％。

铈(Ⅳ)-吐温40-邻苯二酚化学发光体系测定废水中的邻苯二酚

基于在吐温40存在下邻苯二酚与铈(Ⅳ)在酸性介质中发生化学发光反应,建立了测定邻苯二酚化学发光分析法。该法测定邻苯二酚的线性范围为3.0×10-7～5.0×10-5mol/L,检测限为1.0×10-7mol/L,相对标准偏差为3.0%(邻苯二酚浓度为5.0×10-6mol/L,平行测定11次)。用该法测定实验室废水中的邻苯二酚,结果令人满意。

二安替比林对甲基苯基甲烷与Ce(Ⅳ)的显色反应研究

研究了二安替比林对甲基苯基甲烷 (DAp MM)与 Ce( )的显色反应 ,在 H3PO4 介质中 ,DAp MM与 Ce( )生成橙色产物。λmax=485nm,ε=3.53× 1 0 5L·mol-1·cm-1。Ce( )含量在0 .5～ 8.0μg/2 5ml内符合比耳定律 ,该体系灵敏度高 ,选择性好 ,用于镁合金和含锌矿石中微量铈的测定 ,结果满意。

2-乙基己基膦酸单2-乙基己基酯和二(2-乙基己基)磷酸从硫酸介质中协同萃取Ce(Ⅳ)的研究

研究了用2-乙基己基膦酸单-2-乙基己基酯(HEH/EHP,P507)和二(2-乙基己基)磷酸(HDEHP,P204)从硫酸介质中协同萃取Ce(Ⅳ)的机制。结果表明:在HEH/EHP的摩尔分数在0.6时,体系的协萃系数最大。Ce(Ⅳ)以Ce(SO4)0.5HL2A2的形式被萃入有机相,协萃反应为阳离子交换机制。同时还得到了HEH/EHP和HDEHP从硫酸介质中协同萃取Ce(Ⅳ)时,体系的平衡常数及热力学函数如ΔG,ΔH和ΔS等。