Mutual Separation of Rare Earths in Monazite with Cation Exchange Elution Chromatography

Mutual separation of the individual rare earth elements (exception of cerium) in monazite from different districts was investigated by cation exchange elution method. Strong acid type cation exchange resin, Bio-Rad AG 50 Wx8 and eluting solution of a α-hydroxyisobutyric acid (α-HIBA) were used. Radioactivity tagged Eu-152, 154 or Tb-160 were used as radio active indicator for determination of the distribution coefficients by batch method or for the study of column elution conditions. By gradiently increase of the pH values from 3 to 5 in 0.3 M α-HIBA eluting solution, complete mutual separation of individual rare earth elements, exception of Dy and Y, were obtained. Dy and Y could not be separated by this scheme of separation and their elution zones were overlapped. Rare earth mixture samples of monazite from different districts were separated with this scheme and these results were compared. From this comparison followings were noticed; 1. Compositions of rare earth elements in monazite from different districts are evidently not alike. 2. Samples from Brazil and Southwestern Coast of Taiwan are much more alike in their compositions but not for those from Australia and Outskirt Island. 3. Sample from Outskirt Island has higher in contents of heavier rare earths and also Nd was higher than La.     

氟离子选择性电极法测定钍氟各级稳定常数

硫酸体系钍氟各级稳定常数对稀土冶炼生产实践具有重要的指导作用.采用溶解度法测定了室温(25 ℃)下不同酸度的钍氟共存区,采用氟离子选择电极测定不同浓度氟化氢溶液中的游离氟浓度,得到氢氟各级稳定常数.然后根据钍氟共存区图,配制一系列硫酸钍、氢氟酸和硫酸的混合液,测定各溶液中的游离氟浓度,从而得到钍氟各级稳定常数.结果表明,H与F的第1,2级稳定常数分别为k1=664.4,k2=47.9,Th和F的第1,2,3级稳定常数分别为k16.27×105,k2=9.68×104,k3=5.36×104.     

对氯偶氮氯膦光度法连续测定矿石中稀土总量与钪

在一定的条件下,对氯偶氮氯膦(CPA_pC)与等量的15种单一稀土所形成的络合物具有彼此相似的吸光度值。且该试剂也是钪的灵敏显色剂。据此分析特性,连续测定了矿石中稀土总量与钪,分析结果与标准数据基本相符。     

Spectrophotometric Determination of Zirconium in Monazite Sand

A sensitive spectrophotometric method was developed for the determination of zirconium in monazite sand. The zirconium ion was previously separated from the other interfering elements by a 0.5 M thenoyltrifluoroacetone (TTA)-xylene extraction, then determined with Arsenazo III in 9 M HCl medium. Zirconium reacted with Arsenazo III to form an emeraled green coloured complex having maximum absorbance at 665 nm in 9 M HCl medium. The color was stable for at least 2 hours. Effects of time, HCl concentration, gelatine and various ions have been studied. The system confirms the Beer's law over the concentration range investigated. Optimum condition range for measurement in 1.0 cm quartz cell is 0.1–0.5 μg/ml of zirconium. The molar absorptivity is 1.51×10⁵ liter mole^?1 cm^?1. The metal-ligand ratio of 1:4 was confirmed by Job's Continuous Variation method and the conditional stability constant of Zirconium-Arsenazo III Complex in 4 M HCl and 9 M HCl were also determined by this method.     

Determination of 231Pa in Monazite and Other Streams of the Thorium Production Cycle

Monazite (chief source of thorium) which is available in plenty in the beach sands of Kerala, India, contains uranium in the range of 0.25% to 0.35%. An attempt has been made to estimate ²³¹Pa in monazite and the corresponding process stream samples of the thorium production cycle. This paper reports the ²³¹Pa activity in these samples, after coprecipitation of ²³¹Pa on MnO₂ carrier and estimation by -ray spectrometry. The estimation shows about 1000 Bq/kg of ²³¹Pa in monazite. This is the first reported estimate of ²³¹Pa in monazite.     

碱融浸取–离子选择电极法测定固体废物中的总氟

采用氢氧化钠熔融浸取固体废物中的氟,用离子选择电极法测定其中的总氟含量。固体废物样品经氢氧化钠高温熔融后,以热纯水浸取并加入适量的盐酸使溶液呈弱碱性,去除主要干扰离子。测定氟的线性范围为5.00~500μg,线性相关系数r=0.999 6,检出限为12.5 mg/kg。6种类型固体废物样品的加标回收率在90.4%~110.0%之间,测定结果的相对标准偏差为2.3%~4.6%(n=6)。该方法样品预处理简单、重现性好、检出限低,适用于多种固体废物中总氟的测定。     

离子选择性电极电位法测定钼矿石和钨矿石中氟

采用过氧化钠熔融钼矿石、钨矿石样品,乙二胺四乙酸钠和5-磺基水杨酸混合溶液浸取盐分,将样品溶液静置12h,吸取上层清液,以乙二胺四乙酸钠-硝酸钾组成的混合溶液作为总离子强度缓冲剂,控制溶液pH值为5.1,使用pF-1型氟离子选择电极,以饱和甘汞电极作参比电极测定溶液的平衡电位值。采用标准曲线法测定钼矿石和钨矿石中氟。钼矿石标准物质测定值的相对标准偏差(n=11)为3.36%,经4种国家一级钼矿石、钨矿石标准物质的分析验证,测定结果与标准值吻合。     

对-乙酰基偶氮胂作淋洗剂阳离子交换分离及光度测定钍与稀土(铀、钪)

本文提出用显色剂--对-乙酰基偶氮胂作淋洗剂,阳离子交换分离钍与稀土(铀、钪),流出液可直接用光度法测定,将分离和测定结合起来的新方法.操作较简便快速.分离测定了矿石中稀土及钍,结果尚属满意.     

Amperometry with Two Polarizable Electrodes. Chelometric Determination of Rare Earths

Abstract

The method of determining rare earths by chelometric EDTA titration with biamperometric end-point indication using two stationary platinum electrodes was studied. The convenient pH range for the determination of lanthanum is 5.0 – 8.0, for yttrium 3.5 – 8.0 and for ytterbium 3.0 – 8.0. Rare earths have been determined in the presence of iron and thorium. Iron and thorium can be titrated at pH 1.5 – 2.0 and rare earths of the lanthanum group can be determined by successive titration at pH 5.0. Large amounts of rare earths of the yttrium group interfere with the determination of iron and thorium.     

新显色剂二溴对甲基偶氮溴磺光度法测定铈组稀土的研究及应用

研究了新显色剂二溴对甲基偶氮溴磺与铈组稀土的显色反应,在０．６ｍｏｌ．Ｌ＾－１的盐酸介质中,试剂与铈组稀土元素形成２：１稳定的蓝色络合物,其最大吸收波长位于６４２ｎｍ处,稀土含在０－１．０μｇ／ｍＬ范围内符合比耳定律。建立了直接光度法测定钢铁样品中铈组稀土总量的方法。     

流动分析-离子选择电极法测定水中痕量氟化物

基于流动分析-离子选择电极技术,建立了一种测定水中痕量氟化物的分析方法。体系使用注射泵将注入的样品推出,在稳态的条件下进行测定。样品与总离子强度缓冲溶液(TISAB)等体积混合后,采用蠕动泵注入样品,注入量为400L。采用注射泵驱动载流速度快,比蠕动泵效果好。载流为0.05mg/L F-标准溶液,采用奥立龙(Orion)电极,倾斜20°的喷壁型(Wall-jet)流通池。样品之间插入清洗,方法没有交叉携出。在最佳的条件下,方法的线性范围为0.05～1.0mg/L,检出限为0.015mg/L,RSD为1.5%(0.2mg/L)。样品分析频率为30样/h。本方法对质控样品的测定结果令人满意。3个水样的加标回收率为96.8%～104.5%。用4个水样与国标中的手工分析方法进行了对比,在95%的置信区间内,配对t检验结果无显著差异。本方法灵敏度高,分析速度快、试剂消耗少,废液排放量低,适用于水中低浓度样品的分析。     

Studies on the Automated Determination of Total Rare Earths in Al-Re Alloys by Automated Flow Injection Device with DBC-CPA Reagent

The automatic determination of the total rare earths in the aluminium-rare earth alloys was studied by using our recently designed automated flow injection device and the high sensitive and selective rare earth reagent-DBC-CPA (2 -(2-phosphono-4-chlorophen-ylazo)-7-(2,,6-dibromo-4-chlorophenylazo)-1,8-dihydroxy-3, 6 - dis-ulfonaphthalene). The automated flow injection device consists of an Apple Ⅱ microcomputer, two peristaltic pumps and a spectrophoto-meter. It has good automatic degree and high producibility, the sampling volume and rotation velocity of the pumps can be changed continuously and automatically. The total rare earths in aluminium-rare earth alloys were automatically determined at 645nm wavelength in the medium of 1.Omol/L HC1 and 1% H2C2O4 . Fe Cu, Al, Mg, Ni, Zn and Cr don't interfere with the determination and temperature has no effect on the sensitivity in the range of 10-49℃ above zero. The calibration curves for cerium group and yttrium group rare earths are close to each other. T     

钛铁试剂分光光度法直接测定轻稀土中的铈

利用铈的变价以及Ｃｅ（Ⅳ）－Ｔｉｒｏｎ配合物在不同酸度条件颜色的特殊性，建立了无需预先分离而直接测定混合稀土中铈含量的分光光度法，在ＰＨ为９．０条件下，借助空气的氧化，Ｃｅ（Ⅲ）和Ｃｅ（Ⅳ）都与Ｔｉｒｏｎ形成Ｃｅ（Ⅳ）－Ｔｉｒｏｎ配合物。该配合物在ＰＨ为５．０时呈亮黄色，在４３５ｎｍ处有最大吸收。     

稀土与农业

本文简介了稀土农用研究概况、稀土对植物的生理作用、稀土农用的安全性、稀土农用的方法,以及稀土对农业的增产效果等。     

稀土奥贝蠕铁制取工艺及其性能的研究

稀土奥贝蠕铁可用含稀土的蠕化剂及等温淬火工艺稳定地制取,藉助高温扫描电子显微镜,观察并研究了稀土蠕铁奥氏体化过程及稀土奥贝蠕铁随温度升高时组织的变化。用带有加热装置的万能材料试验等土奥贝蠕铁的各种性能进行了系统测定了如抗拉强度、延伸率、冲吉韧性、热膨胀系数及伸长百分率,结果表明,稀土奥贝蠕铁在室温和高温下均有良好的性能。     

Determination of Total and Fluoride Bound Aluminium in Tea Infusions by Ion Selective Electrode and Flame Atomic Absorption Spectrometry

ABSTRACT

Speciation of metallic compunds is important especially for their bioavailability. In this present study fluoride bound aluminium species were determined in tea infusion. Total aluminium was measured using flame atomic absorption spectrometry (FAAS). Free fluoride and total fluoride were measured by fluoride selective ion electrode (FISE) with the assistance of TISAB buffer solution used for adjustment of pH and total ionic strength, and ALCOA buffer solution which decomposes all of the Al-fluoride complexes in solution.

During the studies, the effects of pH and time on the formation of Al-F complexes and interference of some metal ions found in tea infusion such as Al³⁺, Mg²⁺, Fe²⁺, Fe³⁺ and Mn²⁺ on the concentration of free fluoride were investigated. The concentration of each Al-fluoride complexes in tea fusion were determined indirectly by calculation using pF-Mole Fraction Diagram. It was found that 1.13±0.15 mg 1^? of 12.00±0.86 mg 1^? total aluminium is fluoride bound aluminium, which means that appoximately 10% of total aluminium in tea infusion is complexed with fluoride.     

微波消解-氟离子选择电极法测定树叶中氟离子含量

采用微波消解处理样品,氟离子选择电极法测定了树叶中氟离子含量;通过正交实验考察了微波功率、消解时间、固液比、冷却时间等条件对微波消解的影响,对消解试剂和微波消解条件进行了筛选和优化。结果表明,其相对标准偏差小于0.46%,加标回收率在95.5%~103.3%之间。该法简单快速、准确可靠,对测定植物树叶中氟离子含量十分有效。     

Thin Layer Chromatographic Separation of Thorium,Titanium, Zirconium and Some Rare Earths on Cellulose Impregnated Layers

Abstract

The chromatographic saparation of Thorium, Titanium, Zirconium and eight rare earths has been attempted on DBBP, HDEHP and HDEHP-TOPO impregnated cellulose plates using the solvent system MaOH-6N HNO₃?Acatyl acetone (20:15:5). An efficient seperation of 4–5 rare earths on HDEHP-TOPO impregnated plates has been achieved.     

稀土-二安替匹啉甲烷-I~--CHCl_3选择性萃取铁镍合金中稀土元素及其测定

本文提出用CHCl_3选择性萃取稀土-二安替匹啉甲烷-I~三元络合物的方法,从铁、镍合金中分离微量稀土元素,借偶氮胂Ⅲ光度测定。本文较为详细地研究了稀土三元络合物的定量萃取条件及Cu(Ⅱ).W(Ⅵ)对萃取的影响等。在确定的最佳分离及测定条件下,大多数金属离子不干扰测定。方法的测定下限为0.001%RE,相对标准偏差小于8.0%。