Spectrophotometric determination of gold by reaction with molybdate and nile blue in the presence of PVA

A spectrophotometric method for the determination of gold has been developed, based on the reaction of gold(III) with molybdate and nile blue (NB) to form an ion-association complex in the presence of poly(vinyl alcohol). The molar absorptivity at 595 nm is 2.71 × 10⁵ l mol^–1 cm^–1. Beer's law is obeyed over the range 0–16 g of gold per 25 ml. The relative standard deviation evaluated from seven independent determinations of 0.4 g/ml of gold is 2.6%. The limit of detection is 0.011 g/ml. The molar ratio of Au to NB in the complex is established to be 1 2. Over 30 foreign ions were tested for interference; Pt(IV), Sb(III), W(VI) and SiO ₃ ^2– interfered and had to be separated from gold on polyurethane foam. The method can be applied to the spectrophotometric determination of trace amounts of gold in powdered carbon and some ores.     

混合增溶剂对离子缔合物作用的研究

慈云祥等在研究铂、钯、金-碘化钾-丁基罗丹明B显色体系时发现,使用明胶或阿拉伯胶与TritonX-100的混合液,有良好的增溶作用和极好的增敏效应。我们的研究表明:在不少离子缔合物显色体系中,聚乙烯醇-TritonX-100或阿拉伯胶-β-环糊精等混合液,也有很好的增溶(或分散)、增敏和增稳作用。     

I-3-MB-AES体系分光光度法测定面粉中过氧化苯甲酰

在磷酸介质中,过氧化苯甲酰(BPO)氧化I<'->离子形成I<'-><,3>络阴离子,I<'-><,3>络阴离子进一步与亚甲基蓝形成离子缔合物,在烷基聚氧乙烯醚硫酸钠(AES)中,缔合物呈清亮的蓝紫色溶液,以试剂空白为参比,最大吸收波长位于530nm,吸光度A与过氧化苯甲酰浓度呈线性关系,BPO含量在2.0×10<'-...     

IO3--I--亚甲基蓝-阿拉伯胶-聚乙烯醇体系分光光度法测定微量碘

在pH 3.8苯二甲酸氢钾-盐酸介质中,有阿拉伯胶和聚乙烯醇存在下,IO-3氧化I-生成I-3,I-3再与亚甲基蓝形成离子缔合物,缔合物的最大吸收波长为525 nm,表观摩尔吸光系数ε525＝1.32×105 L/(mol·cm),IO-3浓度在0～30 μg/25 mL范围内服从比尔定律. 方法用于碘盐和生物样品中碘的测定,结果满意.     

Extractive spectrophotometric method for the determination of niobium in steels

A strongly coloured complex of niobium with PAR is formed in oxalate solutions and at pH 7.4 can be extracted into nitrobenzene as an ion-association complex with xylometazolonium ion (XMH), with a molar absorptivity of 46300 1 mol^–1 cm^–1 at 545 nm. In contrast to cationic extractants such as tetraphenylphosphonium or tetraphenylarsonium chloride, XMH is an effective extractant over a wide concentration range without any difficulties in either the separation of the phases or the absorbance of the reagent blank. Job's method of continuous variations revealed that the composition of the extracting species as 1 1 1 1 for niobium oxalate PAR XMH. Based on this extraction, a highly sensitive and selective spectrophotometric method for the determination of niobium in various steels, after prior separation of iron, is described. 4-(2-Pyridylazo)resorcinol (PAR) reacts with the niobium tartrate complex in nearly neutral medium to form a red, water-soluble 1 1 anionic complex [1]. PAR is an unselective reagent and one way of improving selectivity is by ternary and ion-association complex formation. The extraction of some highly coloured metal-PAR complexes with tetraphenylarsonium or tetraphenylphosphonium ion has been described [2, 3]. The PAR complex of niobium, which is formed in oxalate solutions has been shown to be extractable by chloroform using tetraphenylarsonium and phosphonium salts [4, 5]. However, in many of these extraction spectrophotometric procedures difficulties arise due to the delay in the separation of the two phases and significant absorbance of the reagent blank solution, particularly when concentrated solutions of reagents are used.The extraction of anionic complexes of Pd, V, and Cr with xylometazolonium (XMH) cation has been reported elsewhere [6–9]. In the present study we have tried to extract Nb(V) and it is observed that 1 1 oxalatoniobium-PAR complex can be extracted with XMH. A method is proposed for the determination of niobium in standard steels.     

A study about pH chemically modified electrodes based on amino-derivatives of naphthalene

On the basis of the study of synergistic sensitizing effect of mixed ionic and nonionic surfactants on a series of color reactions, the synergistic effect of mixed solubilizers (or dispersing agents) was investigated. The systems examined included the mixture of a surfactant (either ionic and nonionic) with soluble macromolecular compounds (e.g. PVA or arabic gum) or with -cyclodextrin. The mixed solubilizers often performed synergism of solubilization, sensitization and stabilization on the systems studied, and for certain cases the selectivity was also improved.     

催化动力学法测定痕量碲的研究

本发现以钯（Ⅱ）作催化剂，碲（Ⅳ）作活化剂，能催化加速次磷酸钠与靛红的褪色反应，建立了一种测定碲的新方法，方法检测限为３．９×１０＾－１１ｇＴｅ（Ⅳ）／ｍｌ，测定范围为０－０．５μｇＴｅ（Ⅵ）／２５ｍＬ，用以测定人发中的痕量碲，获得了满意的结果。     

钯(Ⅱ)与二溴对甲基偶氮磺显色反应的研究

钯(Ⅱ)与二溴对甲基偶氮磺在HNO3介质中形成组成比为1∶2的绿蓝色的配合物,其最大吸收波长位于610nm处,表观摩尔吸光系数ε610=4.0×104L·mol-1·cm-1,钯的质量浓度在0～0.80mg/L范围内符合比尔定律。该法常温下可在水相中直接测定微量钯。并应用于废钯催化剂回收液中钯的测定。     

乙醇在镉试剂与镍的反应体系中的超分子作用

金属离子、有机溶剂与三氮烯偶氮类试剂存在一定的超分子作用,有机试剂与缓冲介质的浓度及种类对显色体系的灵敏度有很大的影响。本文据此建立了乙醇存在下的镉试剂与镍的显色反应的新体系。在pH 9.5的硼砂-NaOH缓冲介质中,在表面活性剂吐温-80存在下,镉试剂与镍反应生成2∶1稳定配合物;吸收波长λmax为504 nm,摩尔吸光系数1.37×105L.mol-1.cm-1;镍含量在0.0~8.0μg/mL范围内符合比尔定律。方法已用于测定铝合金中微量镍。     

The Determination of Trace Amounts of Tellurium and Selenium in Gallium Metal

Abstract

Analytical methods have been developed for the separation, concentration and determination of trace quantities of tellurium and selenium from primary and scrap gallium metal. A chloroform extraction is made of the tellurium diethyldithiocarbamate complex at a pH of 8.5. This extraction, in the presence of ammonium citrate, allows the satisfactory determination of tellurium by emission or atomic absorption spectrohcopy. The limit of sensitivity of the method is 0.5 pg of tellurium in 1.0 gram of gallium (0.5 ppm Te).     

Study of the photophysical behavior of tetrasulfonated metallophthalocyanines in the presence of CdTe quantum dots

Förster resonance energy transfer (FRET) studies were carried out with CdTe quantum dots (QDs) synthesized in aqueous phase and various tetrasulfonated metallophthalocyanines (MPcS₄, M = aluminum ((OH)AlPcS₄), zinc (ZnPcS₄), silicon ((OH)₂SiPcS₄) and germanium ((OH)₂GePcS₄) in a H₂O:MeOH (1:1) solvent mixture. The QDs studied were capped with thioglycolic acid (TGA) or mercaptopropionic acid (MPA) with sizes ranging from 2.3 to 3.7 nm. Non-radiative energy transfer from QDs emission to MPcS₄ complexes was observed. Study of the photophysics of the MPcs in the presence of the QDs revealed high triplet state quantum yields (Φ_T, ranging from 0.41 to 0.85 in the presence of QDs), with corresponding long triplet state lifetimes (τ_T, which ranged from 140 to 610 μs in the presence of QDs) to allow for photosensitized reactions to occur. The efficiency of energy transfer and the donor–acceptor distance between the MPcs and the QDs were also evaluated.     

Study on the Thermodynamic Stabilities of Te-Substituted Di-n-butyltellurium Ylide

SincethediscoveryofphosphoniumylidebyWittig',carbanionsstabilizedbyadjacentfifthorsixthgrouponiumionshavebeendevelopedasavaluablereactiveintermediate.However,despitethegreateffortsinylidechemistryinthepastfewdecades',relativelylittleisknownaboutthethermodynamicstabilitiesofylidecarbanions.Itiswellknowthatthequantitativemeasuresofthecarbanionstabilityhavecontributedagreatdealtothedevelopmentoforganicchemistry,thereforeitshouldbeexpectedthattheknowledgeaboutylidestabilitywillalsoprovidavaluableg…     

镉试剂与银显色反应体系中乙醇的超分子作用及其应用

金属离子、有机溶剂与偶氮类试剂之间存在一定的超分子作用,有机溶剂及缓冲介质的浓度对显色反应的灵敏度有很大的影响。据此建立了乙醇存在下的镉试剂与银的显色反应新体系。在pH9.5的硼砂-NaOH缓冲介质中,表面活性剂吐温-80的存在下,镉试剂与银反应生成2:1稳定配合物。络合物的λmax=518nm,摩尔吸光系数7.01×104L.mol-1.cm-1,银质量浓度0～1.0μg/mL范围内符合比尔定律。方法用于环境水样中银的测定,取得满意效果。     

八乙基金属卟啉的轴向配位反应研究及稳定常数测定

测定了八乙基金属卟啉 (OEP) M中当M=Zn, Cu, FeCl 或 MnCl时在CH2Cl2, N,N-二甲基甲酰胺(DMF), 二甲亚砜(DMSO), 吡啶(Py)等4种不同非水溶剂中的紫外-可见光谱, 探讨了溶剂的性质对八乙基金属卟啉光谱的影响. 结果表明八乙基锌、铁、锰卟啉在CH2Cl2中能够与配位溶剂如DMF, DMSO或pyridine 等发生轴向配位反应生成五配位或六配位的金属卟啉配合物. 用微量光谱滴定法测定了Zn、 Fe、 Mn等金属卟啉和配位溶剂发生轴向配位反应的稳定常数(logK). 讨论了中心金属离子的电负性以及配位溶剂的给电子能力对稳定常数的影响.     

阿莫西林与维多利亚蓝B的显色反应及应用

The color reaction of amoxicillin with victoria blue B was studied.A novel visible spectrophotometric method for the determination of amoxicillin has been established.Under pH 8.50～10.5 condition,victoria blue B reacteds with amoxicillin to form red ion association complex.The maximum absorption wavelength was at 630nm and the apparent molar absorptivity(ε) was 2.67×10~4 L·mol~(-1)·cm~(-1) and the linear ranges was 0～5.5 mg·L~(-1).Amoxicillin obey Beer's law in definite concentration range.The optimum reaction conditions and the methodological precision were studied simultaneity.The method was simple and rapid and sensitive for the determination of amoxicillin.This method has been applied to the determination of amoxicillin is in the city sell amoxicillin medicament is in point and average recovery at 98.2%～101.0%.     

Studies on the mechanism of the Carr-Price blue colour reaction

The reaction of retinoids (retinol, retinyl acetate and anhydroretinol) with Br?nsted acids was studied as a model system for the Carr-Price reaction. The anhydroretinylic cation was characterised by VIS and 2D NMR spectroscopy, including an estimate of the charge distribution and region of bond inversion, observed in a mixture of identified E/Z isomers. Products obtained by quenching with NaOMe-MeOH were identified by HPLC and MS. The classical Carr-Price reaction between retinol (vitamin A) and the Lewis acid SbCl(3) in saturated chloroform solution was reinvestigated by VIS, NMR, EPR, dynamic light scattering and chemical quenching. Whereas product instability and failure to provide informative NMR spectra indicated a radical cation, EPR results excluded free-radical species. Dynamic light scattering experiments, in comparison with model systems, revealed strong aggregation for the Carr-Price complex, rationalizing the low stability, NMR problems and dimerisation observed by chemical quenching. The VIS data support structural similarity of the blue Carr-Price product with the delocalized anhydroretinylic cation, and a detailed structure of the antimony complex is evaluated.     

Palladium(II) chloride catalyzes the cross-coupling reaction of 2,5-bis-(butyltelluro)-furan and 1-alkynes

Palladium(II) chloride catalyzed the cross-coupling reaction of 2,5-bis-(butyltelluro) furan and terminal alkynes yielding both symmetrically and unsymmetrically substituted 2,5-bis-acetylenic furan derivatives. The methodology represents a general and efficient protocol for carrying out the synthesis of furan derivatives with potential biological activities.     

Spectrophotometric study of colour reaction of vanadium(IV) with Chrome Azurol S in the presence of cationic and non-ionic surfactants

The optimum conditions for the formation of complexes of vanadium(IV) with Chrome Azurol S (CAS) in the presence of cationic (benzyldodecyldimethylammonium bromide (ST)) and non-ionic (Triton X-100, Tween 20 and Brij 35) surfactants have been determined. The complexes are formed in weakly acid solution (optimum pH: 4.6, 4.0 and 3.9) and show the absorption maxima at 603, 600 and 598 nm, respectively. The highest sensitivity was obtained for the method based on quaternary system V(IV)-CAS-ST-Triton X-100 due to the higher CAS: V(IV) molar ratio in this complex than in binary and ternary complexes: V(IV)-CAS) and V(IV)-CAS-ST. The molar absorptivity of this system is 8.08 × 10⁴ L/mol cm. The LOD and LOQ values are: 0.006 and 0.02 μg/mL, respectively. Beer’s law is obeyed in the range: 0.02–0.60 μg/mL of V. The precision (RSD = 0.51%) and accuracy (1.9%) are satisfactory. This method has been applied to the determination of vanadium in plant materials.     

The colour reaction of phenols with the Gibbs reagent

Summary Indophenols and indophenolates resulting from the Gibbs reaction were prepared in the pure state and their properties studied under the conditions used in the photometric reactions. The results obtained and previous investigations allowed determination of the optimum conditions for the photometric procedure. Reproducible results are obtained when 2×10^–6–2×10^–5 M phenol reacts with a 30–501 ratio of the reagent. The optimum pH range is 8.0–10.0, obtained with a suitable buffer. It is not possible to use a glycocoll buffer (quantitative reaction with the reagent) and ammoniacal buffers cannot be used for quantitative purposes. If extraction into an organic solvent is necessary, 1-butanol should be used without previous acidification of the reaction mixture. The first step of the colour reaction is the formation of the corresponding quinoneimine. Two molecules of this reactive species react immediately with one molecule of phenol.

---

Zusammenfassung Die Indophenole und Indophenolate, die bei der Reaktion nach Gibbs entstehen, wurden in reinem Zustand dargestellt und ihre Eigenschaften unter den Bedingungen der photometrischen Reaktion studiert. Die erhaltenen Resultate und vorherige Untersuchungen¹ ermöglichten die Definition optimaler Bedingungen für die photometrische Analyse. Reproduzierbare Ergebnisse werden erhalten, wenn 2×10^–6 bis 2×10^–5 M Lösungen von Phenol mit einem 30–501-Überschuß an Reagens umgesetzt werden. Der optimale pH-Bereich ist 8,0 bis 10,0 und wird mit einer geeigneten Pufferlösung eingestellt. Es ist nicht möglich, Glykokoll als Puffer anzuwenden (quantitative Reaktion mit dem Reagens) und ammoniakalische Pufferlösungen können nicht für quantitative Zwecke verwendet werden. Wenn die Extraktion mit einem organischen Lösungsmittel nötig ist, sollte man 1-Butanol ohne vorheriges Ansäuern der Reaktionslösung anwenden. Die erste Reaktionsstufe ist die Bildung von 2,6-Dihalogenchinonimin. Zwei Moleküle dieser reaktiven Verbindung reagieren sofort mit einem Molekül Phenol.

---

---

Dedicated to Prof. RNDr. Arnot Oká, Dr. Sc., member of the Czechoslovak Academy of Science, on the occasion of his 75th birthday.