Titration of phosphonic acid derivatives in mixtures

An analytical procedure is described for the determination of the weak acids phosphonomethyliminodiacetic acid and phosphonomethyliminoacetic acid in their mixtures, and the dissociation constants of phosphonomethyliminoacetic acid are reported.     

Titration of binary mixtures of rare earth metals based on magnetic susceptibility measurements

Gouy balance weighings are used to monitor precipitation titrations of rare earth ions with standardized oxalate solutions. A procedure is described for the analysis of binary mixtures of these compounds. The accuracy of the determinations at the millimolar level depends on the magnetic moments of the components involved but is generally better than ±4%.     

Acid-base titrations by stepwise addition of equal volumes of titrant with special reference to automatic titrations-II Theory of titration of mixtures of acids, polyprotic acids, acids in mixture with weak bases, and ampholytes

A general method for evaluating titration data for mixtures of acids and for acids in mixture with weak bases is presented. Procedures are given that do not require absolute [H]-data, i.e., relative [H]-data may be used. In most cases a very rough calibration of the electrode system is enough. Further, for simple systems, very approximate values of the stability constants are sufficient. As examples, the titration of the following are treated in some detail: a mixture of two acids, a diprotic acid, an acid in presence of its conjugate base, and an ampholyte.     

Relative calcium-binding strengths of amino acids determined using the kinetic method

We have measured the relative calcium-binding energies of amino acids using tandem mass spectrometry of Ca(2+)-bound trimeric amino acids. Although calcium-bound dimeric amino acid complexes coordinated too strongly to allow observation of the two competing dissociation products (calcium-bound monomeric ions) required for analysis of their metal binding affinities using the conventional kinetic method, the Ca(2+)-bound trimeric cluster ions dissociated readily to form dimeric cluster ions through simple ligand losses. The calcium-binding energies were obtained by comparing the ratio of the [Ca(2+)(A(1))(2) - H(+)](+) and [Ca(2+) (A(1))(A(2)) - H(+)](+) ions that dissociated from the [Ca(2+) (A(1))(2)(A(2)) - H(+)](+) ion and the ratio of the [Ca(2+)(A(2))(2) - H(+)](+) and [Ca(2+)(A(1)) (A(2)) - H(+)](+) ions that dissociated from the [Ca(2+)(A(1))(A(2))(2) - H(+)](+) ion, where A(1) and A(2) represent two amino acids. The energies deduced from this analysis represent the relative average binding energies of complexes having the form [Ca(2+)(A(1))(2) - H(+)](+). The relative Ca(2+)-binding strengths of the alpha-amino acid complexes follow the order Cys < Ser < Thr < Ile < Leu < Val < Gly < Ala < Pro < Phe < Met < Tyr < Asn < His < Gln < Trp < Lys < Arg. To our knowledge, this report provides the first example of using kinetic methods to determine the relative binding strengths of divalent metal-amino acid complexes.     

Titration of strong and weak acids by sequential injection analysis technique

A sequential injection analysis (SIA) titration method has been developed for acid-base titrations. Strong and weak acids in different concentration ranges have been titrated with a strong base. The method is based on sequential aspiration of an acidic sample zone and only one zone of the base into a carrier stream of distilled water. On their way to the detector, the sample and the reagent zones are partially mixed due to the dispersion and thereby the base is partially neutralised by the acid. The base zone contains the indicator. An LED-spectrophotometer is used as detector. It senses the colour of the unneutralised base and the signal is recorded as a typical SIA peak. The peak area of the unreacted base was found to be proportional to the logarithm of the acid concentration. Calibration curves with good linearity were obtained for a strong acid in the concentration ranges of 10(-4)-10(-2) and 0.1-3 M. Automatic sample dilution was implemented when sulphuric acid at concentration of 6-13 M was titrated. For a weak acid, i.e. acetic acid, a linear calibration curve was obtained in the range of 3x10(-4)-8x10(-2) M. By changing the volumes of the injected sample and the reagent, different acids as well as different concentration ranges of the acids can be titrated without any other adjustments in the SIA manifold or the titration protocol.     

Analysis of certain mixtures ofα-Amino acids

Summary -Amino acids are determined by reaction with perinaphthindan-2,3,4-trione hydrate to form dihydroxyperinaphthindenone which is titrated with chloramine-T in the presence of acidified bromide and methyl red. The thiol group of cysteine is blocked by cyano-ethylation before determination. Some amino acids can be directly titrated with chloramine-T in the presence of bromide and methyl red, e. g., cysteine (after cyanoethylation), methionine and lanthionine, or in the presence of iodide and starch, e. g., cysteine (after tetrathionate reaction) when concomitant amino acids do not interfere. These methods are used to analyze model mixtures of cysteine with serine, methionine with glycine and cysteine with methionine.

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Analyse bestimmter Gemische von -Aminosäuren

Zusammenfassung -Aminosäuren werden mit Peri-Naphthindan-2,3,4-trion-hydrat umgesetzt, wobei sich Dihydroxyperinaphthindenon bildet, das mit Chloramin T in der Gegenwart von angesäuertem Bromid und Methylrot titriert wird. Die Thiolgruppe des Cysteins wird vor der Bestimmung durch Cyanoäthylierung blockiert. Manche Aminosäuren können unmittelbar mit Chloramin T in der Gegenwart von Bromid und Methylrot titriert werden, z. B. Cystein (nach Cyanoäthylierung), Methionin und Lanthionin, oder in Gegenwart von Jodid und Stärke Cystein (nach Umsetzung mit Tetrathionat), wenn die begleitende Aminosäure nicht stört. Diese Verfahren wurden benutzt, um Modellgemische von Cystein mit Serin, Methionin mit Glycin und Cystein mit Methionin zu analysieren.

     

TLC resolution of enantiomeric mixtures of amino acids

Summary Resolution of enantiomeric mixtures of DL-amino acids (Nine) using silica gel layers impregnated with (-)-bruncine is reported. The solvent system used was Butanol: Acetic acid: Chloroform (3∶1∶4). The diastereomers were formed and hydrolysed, by dilute HCl spray, on the chromatogram only and the amino acids thus resolved were located by ninhydrin spray. The cross resolution possibilities of enantiomers were also calculated.     

某些含氧酸的酸强度与量化参数的相关性

本文利用从头计算法, 采用STO-3G基集计算了某些含氧酸分子的电子结构, 它们的标准几何构型取自已知的实验数据. 将氢、氧原子上的总电荷密度以及氧原子上的亲电子超离域度与实验测得的酸性离解常数相联系, 应用多元回归法, 得到了较好的线性关系.     

Thermal studies on mixtures of aminosalicylic acids with cyclodextrins

The thermal behaviour of the aminosalicylic acids is compared with the behaviour of their 1:1 molar ratio physical and kneaded mixtures with each of three different cyclodextrins (b-, hydroxypropyl-b-, and g-cyclodextrin), using differential scanning calorimetry and thermogravimetry coupled with evolved gas analysis by Fourier transform infrared spectroscopy. X-ray powder diffraction and infrared spectroscopy provided complementary information. Comparison of the effects of the different cyclodextrins on the behaviour of the individual aminosalicylic acid isomers shows that hydroxypropyl-b-cyclodextrin has the greatest interaction with 3-aminosalicylic acid and 5-aminosalicylic acid, followed by g-cyclodextrin, while b-cyclodextrin generally shows the least interaction. For 4-aminosalicylic acid, the effect of g-cyclodextrin seems to be more marked than for 3-aminosalicylic acid and 5-aminosalicylic acid. This revised version was published online in July 2006 with corrections to the Cover Date.     

偏最小二乘线性拟合滴定甘蔗糖蜜中多组分有机酸

将滴定体系调节至pH 2.0,用碱标准溶液滴定至特定pH所消耗滴定荆为测量指标,构建了多组分有机酸滴定数据阵,分别以主成分回归法、偏最小二乘法以及人工神经元网络法进行多组分拟合.结果表明,偏最小二乘法的拟合结果最佳,对混合体系中乙酸、乳酸、草酸、琥珀酸、柠檬酸和乌头酸总量的相对预测均方根误差分别为5.80%、8.88%...     

Nitration of polyhaloalkenes by mixtures of nitric and sulfuric acids

Conclusions The nitration of polyhaloalkenes was carried out under conditions for the complete conversion of nitric acid to the nitronium cation. Butyl esters of -nitrocarboxylic acids were obtained by esterification of the nitration products.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2814–2815, December, 1985.     

Spectrophotometric determination of aromatic and heterocyclic amino acids in mixtures

A procedure for the determination of individual aromatic and heterocyclic amino acids in mixtures was developed with the use of the Vierordt method. Amino acids can be simultaneously determined by this procedure in the concentration range (0.4-3.0) x 10^-3 M. The determination errors for binary and ternary mixtures were no greater than 5 and 10%, respectively. The determination error increases with a decrease in the concentration of a particular component and with an increase in the number of components in the test mixture.     

卤代乙酸在水-DMF混合溶剂中的电离热力学研究

用LKB2277 BioActivity Monitor测定了298.15K时, 乙酸、氯乙酸、溴乙酸和碘乙酸在水-DMF(N, N-二甲基甲酰胺)混合溶剂中的标准电离焓, 计算了相应体系的标准电离熵。用溶质和溶剂相互作用的观点讨论了实验结果。     

Chromatography of substituted benzoic acids with methanol-water-carbon dioxide mixtures.

The impact of the proportion of CO2 concentration in methanol-water-CO2 mobile phases on the separation of several substituted benzoic acids was explored by studying the variation of retention with mobile phase pH in these mixtures. As the amount of CO2 in methanol-aqueous buffer-CO2 mixtures increased, a more basic buffer was needed to control the dissociation of these acids. Differences in terms of retention, separation efficiency and peak asymmetry were shown for substituted benzoic acids with methanol-water-CO2 and methanol-aqueous buffer-CO2 mixtures. Variations of these chromatographic parameters with mobile phase pH were related to the dissociation of these acids and their interaction with methanol-aqueous buffer-CO2 mobile phases and the stationary phase. The addition of a buffer into methanol-aqueous solution-CO2 was an effective means to optimize separations of acidic analytes with high fluidity liquid mobile phases. The substituted benzoic acids had baseline separation in the least amount of time using the high fluidity liquid mobile phases.     

Determination of thorium in zirconium-hafnium mixtures by aromatic polycarboxylic acids

Summary Results are presented for 1,3,5-benzenetricarboxylic (trimesic), 1,2,4-benzenetricarboxylic (trimellitic) and 1,2,4,5-benzenetetracarboxylic (pyromellitic) acids as precipitants for thorium. Trimesic and pyromellitic acids have been found to be better reagents than trimellitic acid. Thorium and zirconium-hafnium mixtures can be separated by precipitating zirconium-hafnium first in 0.5–0.8 N acid solution and then precipitating thorium in the filtrate at 3–4 pH. The separations are quite reproducible. The precipitates in all cases are ignited to the respective oxides. 5–10 mg samples of thorium can be estimated and separated from 10–50 mg samples of zirconium and/or hafnium. Results of investigations on interferences of cations and anions and pyrolysis curves for the decomposition of precipitates are presented.

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Zusammenfassung Als Fällungsmittel fÜr Thorium wurden 1,3,5-Benzoltricarbonsäure (Trimesinsäure), 1,2,4,5-Benzoltetracarbonsäure (Pyromellitsäure) und 1,2,4-Benzoltricarbonsäure (Trimellitsäure) untersucht, wobei die beiden ersten sich als gÜnstiger erwiesen haben. Gemische von Thorium und Zirkonium/Hafnium kÖnnen getrennt werden, indem man zuerst Zr/Hf in 0,5–0,8 n saurer LÖsung fällt und anschlie\end Thorium aus dem Filtrat bei pH 3–4 niederschlägt. Die Trennung ist gut reproduzierbar. Die Niederschläge werden jeweils zu den entsprechenden Oxiden verglÜht. 5–10 mg Th kÖnnen von 10–50 mg Zr und/oder Hf getrennt werden. StÖrungen durch andere Kationen und Anionen wurden untersucht und Pyrolysekurven fÜr die Zersetzung der Niederschläge aufgestellt.

     

Dissolution enthalpy of phosphoric and acetic acids in water-dimethylformamide mixtures

Dissolution enthalpies of phosphoric and acetic acids were experimentally determined (concentration of acid, up to 3 mol/kg) in water—dimethylformamide (DMF) mixtures (molar part of DMF, from 0 to 1) at 298.15 K. Standard dissolution enthalpies of acids in the mixed water-DMF solvent were estimated on the basis of the obtained data.     

Resolution of spectra of mixtures,applied to gaseous formic acids

By appropriate manipulation of FTIR spectra of binary mixtures of monomeric and dimeric formic acids, resolved spectra of the rapidly interconverting species can be recorded. Infrared spectra of the individual compounds were obtained over the range 3700-500 cm⁻¹, from records of equilibrium mixtures of HCOOH/(HCOOH)₂, and of DCOOH/(DCOOH)₂.