The Simultaneous Spectrophotometric Determination of Osmium and Ruthenium

Abstract

A spectrophotometric procedure is described for the simultaneous determination of osmium and ruthenium in the form of bromo complexes. It was found that a blue ruthenium-thiourea complex could be formed in 6.7 M HBr solutions while the osmium could be maintained as the hexabromoosmate complex. Absorption maxima were at 620 μ for the ruthenium complex and at 446 μ for the osmium complex. Molar absorptivities for the ruthenium complex were 2.47 × 10³ at 620 μ and 763 at 446 μ. For the osmium complex molar absorptivities were 328 at 620 μ and 6.81 × 10³ at 446 μ. The method is useable over the range of 5 to 30 ppm with an absolute error of = 1 ppm over the range. Other platinum metals interfere.     

模糊聚类-偏最小二乘光度法同时测定锇和钌

将模糊聚类分析与偏最小二乘相结合，对锇、钌双组份重叠光谱进行解析；较好地解决了校正分析中校准模型的优化问题，提高了分析结果的准确度；研究了锇、钌－ＳｎＣｌ２－乳化剂ＯＰ－阿拉伯树胶（ＡＧ）－丁基罗丹明Ｂ（ＢＲＢ）高灵敏多元离子缔合物显色体系。锇、钌的检出限分别为 ０，６３２ μｇ／Ｌ和 ０．３６８ μｇ／Ｌ，模拟地质样品分析结果的相对误差小于±１０％。     

稳健偏最小二乘光度法同时测定贵金属元素锇和钌

本文将稳健偏最小二乘法用于贵金属元素锇、钌的光度法同时测定，较好地解决了实际校准模型由于实验误差偏离正态分布使计算结果的精度遭到破坏的问题。     

Thionitrosyl Complexes of Ruthenium and Osmium

The ruthenium trichloride hydrate and osmium tricholide react with (NSCl)₃ in presence of triphenylphosphine and triphenylarsine to give thionitrosyl complexes M(NS)Cl₃L₂ (M) ? Rn, or Os; L ? PPh₃ or AsPh₃.     

Rapid Spectrophotometric Determination Of Osmium With Cyclohezane 1,3-Dione Bisthiosemicarbazone Monohydrochloride: Simultaneous Determination of Osmium and Platinum

Abstract

A simple, sensitive and rapid spectrophotometric method has been developed for the determination of osmium using cyclohexane 1,3-dione bisthiosemicarbazone mono-hydrochloride (1,3-CHDT.HCl). The method is based on the instantaneous colour reaction between 1,3-CHDT. HCl and osmium(VIII) in sodium acetate—acetic acid buffer medium (pH range 3–6). The osmium complex shows maximum absorbance at 375 nm and considerable absorbance at 510 nm. Although the complex formed between platinum(IV) and reagent (1,3-CHDT.HCl) shows maximum absorbance at 375 nm, it does not show any absorbance at 510 nm. Simultaneous determination of osmium and platinum is carried out when present alone and in presence of other foreign (associated) ions. Some physico-chemical and analytical characteristics of osmium and platinum complex are described. Interference of various foreign ions have studied and osmium is estimated selectively in the presence of constituents of platinum ores.     

氢还原重量法测定三氯化钌产品中钌的含量

建立了氢还原重量法测定三氯化钌产品大样中钌含量的新方法,研究并优化了测定条件,结合原子吸收光谱法(AAS)、电感耦合等离子体原子发射光谱法(ICP-AES)和氯化铵纯度考察了杂质元素对了分析结果的误差影响。结果表明,钌含量为0.3~0.6g的三氯化钌与5~7g氯化铵能完全形成(NH4)2RuCl6配合物,于约100℃烘干水分、350℃分解铵盐、750℃氢还原为海绵钌和105℃干燥水气的条件下,测定3.94%,5.88%,7.32%,9.47%,10.84%和12.93%含量的钌,极差、标准偏差(S)、相对标准偏差(RSD,n=22)和重复性限(r)分别为±0.01%,0.0030%~0.0050%,0.0369%~0.0761%和0.008%~0.014%。样品加标回收率99.96%~99.98%。方法的结果准确,精密度好,且与YS/T562—2009标准分析方法的吻合。     

A Radiochemical Method for Selective Determination of Traces of Lead

Abstract

A very simple and rapid radiochemical method for the determination of 0.01–1 meg of lead has been developed. It consists of adding carrier-free ²¹²Pb to the analysed sample, followed by shaking with a standard lead diethyldithiocarbamate solution in carbon tetrachloride. The amount of non-active lead in the sample is determined from activities of the organic and aqueous phases. A 10-fold excess of bismuth and more than 50–100-fold excess of other metals extractable as diethyldithiocarbamates do not interfere in the determination.     

A Radiochemical Method for Selective Determination of Traces of Lead

A very simple and rapid radiochemical method for the determination of 0.01—1 mcg of lead has been developed. It consists of adding carrier-free ^{2 1 2} Pb to the analysed sample, followed by shaking with a standard lead diethyldithiocarbamate solution in carbon tetrachloride. The amount of non-active lead in the sample is determined from activities of the organic and aqueous phases. A 10-fold excess of bismuth and more than 50–100-fold excess of other metals extractable as diethyldithiocarbamates do not interfere in the determination.     

Phosphonium-Ring-Fused Bicyclic Metallafuran Complexes of Ruthenium and Osmium

Metallafuran complexes with a fused five-membered phosphonium ring were synthesized from reactions between terminal ynones HC≡C(C=O)R and cis-[Ru/Os(dppm)₂Cl₂] (dppm=1,1-bis(diphenylphosphino)methane). A metal–vinylidene-involving pathway was found to be an energetically feasible formation mechanism for these complexes. These phosphonium-containing metallafurans, like many phosphonium-functionalized drugs, have the ability to induce mitochondrial dysfunction. They also exhibit stronger cytotoxicity against several human cancer cell lines in comparison with their metal precursors and the classic anticancer drug cisplatin. Overall, this work provides structural and mechanistic insights for the rational design of functional metallacycles via activation of alkynes by Ru^II and Os^II centers.     

Ultratrace Osmium,Ruthenium and Lead in Airborne Particulate Matter: Peak Area as Instrumental Datum to Improve Their Simultaneous Voltammetric Determination

Peak area as instrumental datum for determining the concentration of metals in solution instead of peak height is proposed for the simultaneous voltammetric determination in particulate matter of ultratrace Os(VIII), Ru(III) and Pb(II), species linked to vehicle emissions. In the case of species present at ultratrace concentration level or having low reversibility degree of the electrodic processes, the employment of peak area, instead of peak current, permits to achieve limits of detection lower even more of one order of magnitude. The method is based on the catalytic current of the Os(VIII)‐, Ru(III)‐ and Pb(II)‐bromate system by differential pulse voltammetry. 0.3 mol L^?1 acetate buffer pH 4.5+6.9×10^?2 mol L^?1 NaBrO₃+2.3×10^?4 mol L^?1 EDTA‐Na₂ was employed as the supporting electrolyte. For all the elements, the accuracy, expressed as relative error e%, and the precision, expressed as relative standard deviation s_r%, were satisfactory being lower than 6 %. To better validate the analytical procedure, a comparison with spectroscopic (electrothermal atomic absorption spectroscopy, ET‐AAS) is also reported.     

Sequential Voltammetric Determination of Ultratrace Osmium,Ruthenium and Iridium. Application to Superficial Water

The present work, regarding the determination of ultratrace Os(VIII), Ru(III) and Ir(III) in superficial waters is an interesting example of the possibility to simultaneously, or better sequentially determine each single element in real samples by voltammetry. The method is based on the catalytic current of the Os(VIII)‐ and Ru(III)‐bromate systems by square wave voltammetry and on the Ir(III) determination by square wave catalytic adsorptive stripping voltammetry. 0.5 mol L^?1 acetate buffer pH 4.9+7.7×10^?2 mol L^?1 NaBrO₃ and 0.5 mol L^?1 acetate buffer pH 4.9+7.7×10^?2 mol L^?1 NaBrO₃+2.3×10^?5 mol L^?1 cetyltrimethylammonium bromide (CTAB) +0.2 mol L^?1 KCl were employed as the supporting electrolytes. The analytical procedure was verified by the analysis of the standard reference materials: Sea Water BCR‐CRM 403 and Fresh Water NIST‐SRM 1643d. For all the elements, the accuracy, expressed as relative error e (%), was satisfactory, being lower than 6 %, while precision as repeatability, expressed as relative standard deviation, s_r (%), was generally lower than 5 %. Once set up on the standard reference materials, the analytical procedure was transferred and applied to superficial water sampled in proximity to superhighway and in the Po river mouth area.     

Preparation and Crystal Structures of Ruthenium and Osmium Oxide Tetrahalides

RuOF₄ as the highest valence oxide fluoride exist as a molecular compound (a = 606.0(1), b = 836.1(1), c = 626.3(1) pm, β = 91.637(3), Z = 4; P2₁/n) as well as fluorine bridged polymer (a = 547.7(2), b = 928.5(3), c = 1252.4(3) pm, Z = 8, P2₁2₁2₁). A reproducible method for pure, deep blue OsOF₄ is given. Pure OsOF₄‐I is isostructural to the fluorine bridged polymeric RuOF₄ (a = 554.6(1), b = 955.4(2), c = 1278.4(2), Z = 8, P2₁2₁2₁). OsOF₄‐II is also a fluorine bridged polymer (a = 537.8(2), b = 1274.8(4), c = 555.2(2), β = 117.716(6)°, Z = 4, P2₁/c). OsOCl₄ again is a molecular species (a = 938.9(2), b = 561.3(1), c = 1192.0(2), β = 109.944(4)°, Z = 4, P2₁/c).     

氢还原重量法测定亚硝酰硝酸钌溶液中的钌含量

采用盐酸前处理样品,干燥后通氢还原纯化,建立了氢还原重量法测定亚硝酰硝酸钌溶液中的钌含量的方法.结果表明,在称样量为4.0 g、盐酸加入量3 mL,程序升温750℃,保温90 min条件下,测定结果最好.测定钌含量为5.50％、10.89％ 的两种样品,两种样品钌含量分析结果的极差分别为0.11％、0.16％,相对标准...     

高碘酸盐氧化耐尔蓝动力学光度法测定锇

在硫酸介质和热水浴中 ,Os( )对高碘酸盐氧化耐尔蓝有催化作用。研究了反应速率对酸度、浓度、温度和离子强度的依赖关系 ,采用 0 .0 1 0mol/ L硫酸 ,反应的灵敏度随温度升高而增大 ,反应速率对反应混合物的离子强度依赖较小。线性范围为 0～ 0 .2 5μg/ 2 5m L;检出限为 8.0 2× 1 0 -5 μg/ m L;对质量浓度为 0 .1 0 μg/ 2 5m L 的 Os( )测定的相对标准偏差为 1 .0 2 % ( n=1 1 ) ;导出了催化反应的动力学方程 ;探讨了反应机理。4 0 0倍量以上常见金属离子不干扰锇的测定 ,1 0倍量以上的 Ru( )、Fe3 +有干扰。本法已用于贵金属冶金样品中锇的测定。     

Simple and Simultaneous Method for Determination of Palladium(II) and Ruthenium(III) using Second-Order-Derivative Spectrophotometry

Abstract

A simple, sensitive, and selective second-order-derivative spectrophotometric method has been developed for the simultaneous determination of palladium(II) and ruthenium(III) using 2-hydroxy-3-methoxy benzaldehyde thiosemicarbazone (HMBATSC) as a chromophoric reagent. The reagent (HMBATSC) reacts with Pd(II) and Ru(III) at pH 3.0, forming soluble yellowish green and dark brown species, respectively. Palladium and ruthenium present in the mixture were simultaneously determined without solving the simultaneous equations by measuring the second derivative amplitudes at 445 nm and 385 nm, respectively. Further, the Beer's law was obeyed in the range 0.21–12.78 µg mL^?1 and 0.25–13.42 µg mL^?1 for Pd(II) and Ru(III), respectively. A large number of foreign ions did not interfere in the present method. The proposed method was successfully applied for the determination of palladium in hydrogenation catalysts and ruthenium in water samples.     

A Method to Assess Radiochemical Purity of Compounds Measured by Radioimmunoassay

Abstract

A method is described for assessing radiochemical purity of compounds measured by radioimmunoassay. This method is applicable in cases when chromatography is used prior to the radioimmunoassay proper. In individual fractions of the chromatographic zone containing the compound assayed, both radioactivity (e. g. in DPM) and mass (e. g. in pg) are measured. The measurement of mass is performed using radioimmunoassay. Radiochemical purity is assumed, if the radioactivity/mass ratio (specific activity) in individual fractions of the zone is constant. The constancy of specific activity is tested statistically using a regression analysis. A radioimmunoassay of progesterone in a blood plasma pool collected during the follicular phase of the menstrual cycle was used to demonstrate the practical features of the assessment of radiochemical purity. Radiochemical pure progesterone could be obtained only after repeated chromatography. Purification to radiochemical purity resulted in a significantly decreased estimate of progesterone contents in the plasma pool investigated. A value of 344 pg/ml was obtained, in contrast to the value of 422 pg/ml found prior to the repeated chromatography. The former value can be considered an accurate and valid estimate.     

The Determination of Co in Plant Materials by Radiochemical Neutron Activation Analysis

The influence of irradiation conditions on the results of Co determination in plant samples by radiochemical neutron activation analysis (RNAA), after the conventional and microwave assisted wet digestion, has been investigated. Nine CRMs of botanical origin were examined. The study has demonstrated that the effectiveness of mineralization depended significantly on the kind of sample and the irradiation conditions. When analyzed CRMs were subjected to long-term irradiation in a high neutron flux, the mineralization using the microwave technique was necessary to obtain the correct results of Co determination in some of the plant samples. It has been proved that microwave digestion in a mixture of HNO₃+H₂O₂+HF should be a standard method of wet ashing, independent on matrix and irradiation conditions.     

Ruthenium and Osmium Podate Cyclodextrins with Dual-function Recognition Sites for Luminescent Sensing

A multifunctionalised podand cyclodextrin ligand, β-CD-(urebpy)⁷, with urea--bipyridine binding sites leads to ruthenium and osmium, {Ru[β-CD-(urebpy)⁷]}[PF⁶]² {Os[β-CD-(urebpy)⁷]}[PF⁶]², cyclodextrins. The bipyridine ligands are preorganised by the cyclodextrin cavity encapsulating the ruthenium and osmium core to give photoactive metallocyclodextrins. The podate cyclodextrin complexes show characteristic ruthenium and osmium tri-bipyridine luminescence. It is demonstrated that the ruthenium cyclodextrins participate in sensing schemes through both the cyclodextrin cavity and the urea cage at the bottom of the cyclodextrin rim. Luminescence quenching of the ruthenium emission is observed by addition of anthraquinone guests in the cyclodextrin cavity or addition of dihydrogen phosphate anion.