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。     

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4.0g、盐酸加入量3mL,程序升温750℃,保温90min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%,相对标准偏差(RSD,n=7)分别为0.66%、0.52%,与其他标准分析方法相比,测定结果的准确度和精密度更好。     

固绿FCF催化动力学光度法测定痕量钌

研究了钌(Ⅲ)催化高碘酸钾氧化固绿FCF褪色反应的反应条件, 测定了该反应的反应级数和表观活化能, 并建立了测定钌的新动力学光度法. 在选定实验条件下, 非催化反应体系与催化反应体系在633 nm波长处的吸光度差值与钌(Ⅲ)的质量浓度在0～0.001 μg/mL及0.001～0.0025 μg/mL范围内有良好的线性关系, 检出限为 9.53×10-11 g/mL. 对0.001 μg/mL钌(Ⅲ)测定11次标准偏差为1.7%, 方法的选择性好, 灵敏度高, 可用于钌精矿及合成样中痕量钌的测定.     

电感耦合等离子体发射光谱法测定三氯化钌溶液中杂质元素含量

建立电感耦合等离子发射光谱仪测定三氯化钌溶液中杂质元素含量的方法. 通过加入氧化剂将钌基体转化为四氧化钌挥发以消除基体干扰,优化了氧化剂、酸度、测定谱线等试验条件,结果表明,各杂质元素测定结果相对标准偏差（RSD,n=7）均小于5.00%,方法加标回收率为90.0%~106.0%. 方法准确度高,重复性好,能满足实际生产需求.     

氢还原重量法测定氯化钯产品中的钯含量

建立了氢还原重量法测定氯化钯产品钯含量的新方法,系统研究了测定条件,结合ICP-AES法考察了杂质元素对了分析结果的误差影响。结果表明：含钯量约3 g的氯化钯于750 ℃氢还原为海绵钯和105 ℃干燥水气的条件下,测定59.78%、59.98%和60.03%的钯含量,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%、0.0047%～0.0050%、0.0079%～0.0083%和0.009%～0.014%。样品加标准回收率99.98%。本法结果准确、精密,且与GB/T 15072.4-2008标准分析方法的吻合。     

阻抑动力学光度法测定痕量钌

在硫酸介质中,钌(Ⅲ)对高碘酸钾氧化甲基绿褪色反应具有显著的阻抑作用,从而提出了一种阻抑动力学光度法测定痕量钌(Ⅲ)的方法。优化的试验条件如下:①0.01mol.L-1高碘酸钾溶液用量为1.40mL;②1×10-3 mol.L-1甲基绿溶液用量1.50mL;③反应温度为80℃;④反应时间为10min。钌(Ⅲ)的质量浓度在0.04～64μg.L-1范围内与ΔA呈线性关系,检出限(3s/k)为8.5ng.L-1。方法用于活性炭和分子筛中痕量钌(Ⅲ)的测定,测定值的相对标准偏差在1.6%～2.2%之间,加标回收率在98.6%～100%之间。     

甲苯胺蓝指示反应动力学光度法测定痕量钌

在磷酸和热水浴中 ,钌 (Ⅲ )对高碘酸钾氧化甲苯胺蓝的反应具有催化作用 ,据此建立了测定钌的新催化光度法。钌在 0～ 0 .0 5 0 μg/ 2 5ml范围内与催化反应速率有良好的线性关系 ,检出限为 5 .5 3× 10 - 5μg·ml- 1。对 0 .0 30 μg/ 2 5ml钌 (Ⅲ )测定的相对标准偏差为 2 .0 % (n =11)。该催化反应对钌 (Ⅲ )和甲苯胺蓝分别为一级反应 ,其表观活化能为 5 0 .2 6kJ·mol- 1。试验了 4 0多种共存离子的影响 ,大多数的常见离子不干扰。该方法用于岩矿和冶金产品中钌的测定 ,相对标准偏差为 2 .1%～ 2 .4 % ,标准加入回收率为 10 0 .1%～ 10 5 .4 %。     

藏红T催化光度法测定痕量钌

在H2 SO4 和热水浴中 ,Ru(Ⅲ )催化KIO4 氧化藏红T褪色 ,由此建立了测定钌的新催化光度法。钌质量浓度在 0～ 0 0 0 32 μg mL范围内符合比尔定律 ,检出限为 3.3× 1 0 -8g L。对 0 .0 0 2 0 μg mLRu(Ⅲ )测定的相对标准偏差为 1 .7% (n=1 1 )。催化反应的表现活化能为 38.2kJ mol。催化反应对Ru(Ⅲ )和藏红T分别为一级反应。试验了 40多种共存离子的影响 ,允许 2 0 0倍量的Ag+、Pt(Ⅳ ) ,2 0倍量的Pd(Ⅱ )、Ir(Ⅳ )及Cu2 +存在。该方法可用于岩矿和冶金产品中钌的测定 ,相对标准偏差为 1 .1 %～ 2 .4 % ,标准加入回收率为 1 0 0 .3%～ 1 0 1 .5 %。     

橙黄G催化动力学光度法测定痕量钌

研究了钌(Ⅲ)催化KIO4氧化橙黄G(OG)褪色反应的反应条件,测定了该反应的反应级数和表现活化能,并建立了一个测定钌的新动力学光度法。在选定的实验条件下,非催化反应体系与催化反应体系在470nm波长处的吸光度差值与钌(Ⅲ)的质量浓度在0 50～6 0ng/mL范围内有良好的线性关系,检出限为4.4×10-8g/L。对2 0ng/mL钌(Ⅲ)测定11次的相对标准偏差为1 4%。方法可用于冶金产品及岩矿中痕量钌的测定。     

钌(Ⅲ)-过硫酸钾-氨基黑10B体系催化分光光度法测定微量钌的研究

本文首次发现钌(Ⅲ)对K_2S_2O_8氧化氨基黑10B褪色反应有显著催化作用并以此反应为指示反应建立了测定微量钌的催化分光光度法。该方法的检测限为0.02μg/ml,在0.030～0.30μg/ml范围内呈线性关系。该方法已用于贵金属精矿及氯化渣中微量钌的测定,结果令人满意。     

钌配合物断裂DNA及其机理研究

DNA是遗传信息的携带者和基因表达的物质基础,金属配合物与DNA的相互作用研究受到广泛关注,成为生物无机化学的重要研究内容之一.与其他类型金属配合物相比,钌配合物具有良好的热力学稳定性以及丰富的光化学、光物理和氧化还原特性,其作为DNA断裂试剂也引起人们的极大兴趣.以近年一些代表性的研究工作为例,本文对钌配合物在DNA断裂作用机制方面的研究进展进行了综述.     

Resolving ruthenium: XPS studies of common ruthenium materials

X‐ray photoelectron spectroscopy (XPS) utilising monochromatic Al Kα radiation has been employed to study metallic ruthenium and the catalytically and technologically important ruthenium compounds RuO₂, RuCl₃, Ru(NO)(NO₃)₃ and Ru(AcAc)₃. The results improve on the accuracy of already published Ru(3d) binding energies, expand known Ru(3p) binding energies and also report spin‐orbit splitting for the core levels. For RuO₂, the difference between anhydrous and hydrated samples is explored, and the effect on curve fitting such spectra is discussed. Analysis of RuCl₃ has allowed, for the first time, the positive identification of Ru(OH)₃ by XPS. Copyright © 2015 John Wiley & Sons, Ltd.     

Homogeneous catalysis by ruthenium carbonyl clusters

The historical background of and the incentive for using ruthenium carbonyl clusters as homogeneous catalysts are outlined. Keeping in view the possible solutions the uncertainties arising from declusterification and metal colloid formation are discussed. All ruthenium cluster-catalysed reactions are broadly classified as reactions with or without carbon monoxide as one of the reactants and the basic differences between such reactions are highlighted. Some of the factors of special relevance to cluster-catalysed reaction systems are mentioned. The reactions involving carbon monoxide are then discussed. These include water-gas-shift reaction, carbon monoxide hydrogenation, hydroformylation, reductive carbonylation of nitrobenzene and other carbonylation reactions. Hydrogenation, transfer hydrogenation, isomerisation and a few other reactions are then discussed. For all these reactions, special emphasis is laid on well-characterised cluster complexes that have been proposed as catalytic intermediates. Finally an attempt has been made to identify the path that future research in cluster catalysis is likely to follow.     

19-Electron arenecyclopentadienyl complexes of ruthenium

A series of are necyc lope ntadienyl complexes,i. e., [Ru(⁵-c₅R₅)(⁶- are ne)]⁺ (1, R= H, arene = C₆H₆; 2, R = Me, arme = C₆H₆; 3, R = H, arctic = C₆H₃Me₃; 4, R = Me, arene = C₆H₃Me₃; 5, R = H, arene = C₆Me₆; 6, R = Me, arene = C₆Me₆) was studied by cyclic voltammetry. These compounds are capable of both oxidation and reduction. The reduction potential values depend on the number of methyl groups in the complex. Reduction of benzene complexes I and 2 by sodium amalgam in THF leads to the formation of decomplexation products, the addition of hydrogen to benzene, and dimerization of the benzene ligands. Both chemical and electrochemical reductions of mesitylene complexes3 and4 result in dimeric products [(⁵-C₅R₅)Ru(-⁵;⁵-Me₃H₃C₆H₃Me₃)Ru(⁵-C₅R₅)] (14, R = H; 15, R = Me). The action of sodium amalgam on compound5 gives products of hydrogen addition to both hexamethylbenzene (17) and cyclopentadienyl (18) ligands along with the major product, the dimer [⁵-C₅H₅)Ru(-⁵; ⁵-Me₆C₆C₆Me₆)Ru(⁵-C₅H₅)] (16). In contrast to5, its permcthylated analog 6 is only capable of adding hydrogen to the hexamethylbenzene ligand.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1691–1697, July, 1996.     

Kinetic analysis of the hydrogenolysis of propane on ruthenium catalysts

The dependence of rates of propane hydrogenolysis on temperature and H₂ pressure have been modelled, using a rate expression based on Langmuir-Hinshelwood formalism. Dedicated to Professor Pál Tétényi on the occasion of his 70th birthday     

Surface reactivity of carbon monoxide with different gases on ruthenium film under UV illumination

Some photocatalytic reactions on a Ru film, where carbon monoxide participates as a reactant have been studied by means of mass spectrometry. Under UV irradiation carbon monoxide is oxidized to carbon dioxide if treated with oxygen. It is transformed to methanol in the presence of hydrogen, and in mixture with water gives hydrocarbon species.     

Competitive hydrogenations over a ruthenium catalyst

Hydrogenations of three individual substrates (-methylstyrene, benzaldehyde, cyclohexanone) were carried out on a ruthenium catalyst. On the basis of these results, selectivities of competitive hydrogenations of -methylstyrene-benzaldehyde, benzaldehyde-cyclohexanone and -methylstyrene-cyclohexanone binary mixtures were evaluated. It was shown that the reactivity of individual substrates could be substantially different when hydrogenated competitively with another compound in a binary system.     

Electrochemical study of allylbenzene and allylcyclohexadienyl complexes of ruthenium

Cyclic voltammetry has been used to study the electrochemical behavior of RuCl(³-C₃H₅)(⁶-C₆H₆) (1), [Ru(PPh₃) · (³-C₃H₅)(⁶-C₆H₆)]BF₄ (2), and Ru(PPh₃)· (³-C₃H₅)(⁵-C₆H₇) (3); the latter was prepared by reacting2 with LiAlH₄. The reduction of1 and2 gives the 19-electron complexes1 ^–. and 2^·, whereas oxidation of3 gives the 17-electron complex3 ^+·. The reactivities of1 ^–·,2 ^·, and3 ^+· are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1126–1128, June, 1993.