Determination of Strong Acid in Air-Borne Matter

Abstract

A titration variant for determination of strong acid in air-borne matter with Gran's plot method is proposed. The procedure can be applied to the titration of non sufficiently acidic samples containing weak acids as NH₄ ⁺, HSO₄ ^? and protolyzable ions. Interferences due to the presence of these species are evaluated.     

Potentiometric titration of trace amounts of mercury after a preliminary separation by a reduction method

Isolation and concentration of mercury by reduction of mercury(II) with acidic tin(II) chloride solution and absorption of mercury vapour in acidic permanganate solution is combined with potentiometric titration with dithiooxamide. The simple procedure is applicable to 5–100 ppb mercury in 1-dm³ samples. Recoveries from organomercurials are discussed.     

Water-soluble modified chitosan and its interaction with a polystyrenesulfonate anion

The selective alkylation of primary amino groups of polysaccharide is conducted through the interaction of chitosan with glycidyltrimethylammonium chloride with introduction of the quaternized amino group into every alkylated unit, thereby ensuring a positive charge and solubility of the polymer over the entire pH range. The structure of the modified chitosan is studied via FTIR spectroscopy and ¹³C and ¹H NMR measurements. On the basis of the potentiometric titration of solutions of the parent polysaccharide, its modified derivative, and their mixtures with the polystyrenesulfonate anion, as well as ζ-potential measurements and turbidimetric titration of polymer mixtures, it is demonstrated that the secondary amino group of the complexed modified chitosan can be protonated in weakly acidic solutions. This behavior is of particular importance for the design of biocompatible and biodegradable vehicles suitable for the delivery of genetic material and drugs to cells.     

Potentiometric studies on thioacetamide by means of a sulphide ion-selective membrane electrode

The sulphide ion-selective electrode has been found to be applicable to the determination of thioacetamide in the concentration range of 10^-1–10^-3 M by direct potentiometry and titration with silver nitrate. The effects of the acid and alkali content of the solutions on the titration reaction have been studied. In alkaline and slightly acidic solutions the product of the reaction is silver sulphide; in solutions in which the acid concentration exceeds 0.5 M, a precipitate of silver thioacetamide is formed. If the alkali concentration of the solution is lower than that corresponding to the amount of acid formed during the titration, another potential jump occurs before the end-point owing to the decrease of sulphide'concentration governed by hydrolysis.     

Determination of99Tc-DPD complex composition and valence states of technetium

DPD (2,3-dicarboxypropane-1,1-diphosphonic acid) forms two complexes with⁹⁹Tc, previously reduced by Sn(II): with _max at 410 nm (pH 3–7), and at 515 nm (pH 5–9.6). By Job's method, formation of complexes with DPD:Tc molar ratios of 21 and 23 was found in acidic medium (pH=3). In order to determine the valence states of Tc in the complex, taking into account that formation of⁹⁹Tc-DPD complex does not occur in absence of a reducing agent (here divalent tin), the redox potentiometric titration method was applied. In acidic medium (pH=3), Tc was reduced to Tc(III) by Sn(II), while in presence of DPD to Tc(IV). In strongly alkaline medium (pH>13) the situation was reverse: Tc(III) was formed in the DPD complex, while Tc(IV) in absence of the ligand. In slightly alkaline medium (pH about 8) in both cases (with or without the ligand) TC(III) was obtained at the titration end point. This phenomenon can explain the dependence of^99mTc-radiopharmaceutical complexes on the sequence of reagent addition. These conclusions are very important for^99mTc-DPD radiopharmaceutical solutions used in diagnostic nuclear medicine for skeletal imaging.     

Sodium meta-vanadate as volumetric reagent: Iodine monochloride method

In hydrochloric acid medium sodium meta-vanadate was used as a volumetric reagent for the determination of copper, zinc, cobalt, mercury, and lead. Cu⁺², Zn⁺² and Co⁺²were precipitated as complex mercurythiocyanates, Hg⁺² as mercuric zinc thiocyanate and Pb⁺² as Iodide. The thiocyanates were dissolved in concentrated hydrochloric acid and titrated against standard sodium meta-vanadate solution in the presence of iodine monochloride as a pie.oxidizer and catalyst. In titration of the iodide against the meta-vanadate. it was not necessary to add iodine monochloride to the titrant because it is formed during the titration. Chloroform was used as an indicator. It was pink owing to the liberation of iodine during the titration and became pale yellow at the end-point because of the formation of iodine monochlonde.     

End-point construction and systematic titration error in linear titration curves-precipitation reactions

The systematic titration error which is introduced by the intersection of tangents to hyperbolic titration curves is discussed for precipitation reactions. A simple expression for the systematic titration error is derived, and S/C_x² is proposed as a measure of the sharpness of the titration curve. The effects of the conditional solubility product (S), the concentration of the unknown component (C_x), and the ranges used for the construction of the end-point, are considered. A graphical method is presented for the selection of pairs of ranges which result in small systematic titration errors. For equal values of S/C_x² and 1/KC_x, the optimum combinations of ranges are different for precipitation and complexation titrations. The differences are not large for values smaller than about 0.002. For titration curves with a reversed L-shape, the error is calculated when the end-point is constructed by the intersection of the tangent to the second branch of the curve with volume axis; in this case equal ranges result in the same titration error for equal values of S/C_x² and 1/KC_x. The systematic titration error is equal to -S/C_x² when the tangent to the curve is taken at f_a = 3.0.     

Use of a Tensammetric Wave for the End-Point Detection in Chelatometry

Abstract

A new method for the end-point detection in complexometric titration using a tensammetric wave of organic reagents such as oxine and alizarin complexone (ALC) was studied. The tensammetric wave of these reagents disappears by their chelate formation and reappears by the liberation of free indicator during the exchange reaction between indicator chelate and EDTA. This mechanism is utilized for the end-point detection in complexometric titration of metals. Since the sensitivity of tensammetric wave is extremely high, very sharp end-point can be obtained for the titration of metals even in the concentration of 10^?5M.     

Méthode pratique de dosage ampèrométrique du manganèse

A practical method is described .for thu determination of manganese by ampcrometnc titration.The Mn⁺² ion is oxidized quantitatively into Mn⁺³ (complex formation) by titration with permanganate in approximately neutral pyrophosphate solution. We have found that the end point of this Litration appears both very clearly and accurately by using a most simple electiometric device. A. platinum and a silver wire dipping in the solution are connected directly to a pointer galvanometer. The so revealed current remains very low during the titration and suddenly increases at the equivalence point.Tins titration can be effected quickly. The growing instability of the pointer usefully warns of approaching end point. There is practically no interference from foreign ions and theercfore the method can be applied widely and easily.     

Anionic synthesis and characterization of ω‐carboaldehyde‐functionalized polybutadienes and polyisoprenes

Attempted preparation of ω‐formyl‐functionalized polydienes by termination of poly(butadienyl)lithium and poly(isoprenyl)lithium with 4‐morpholinecarboaldehyde resulted in 73 and 38% dimer formation (SEC), respectively, under conditions that quantitativey produced ω‐formyl‐functionalized polystyrene. Dimer formation was attributed to postfunctionalization, base‐catalyzed, aldol‐type condensation based on FTIR and ¹H‐NMR analysis of the dimer products. High yields (>97%) of ω‐formyl‐functionalized polydienes were formed by workup using acidic methanol; quantitative functionalization resulted from end capping the polymeric organolithium chain ends with 1,1‐diphenylethylene prior to the functionalization reaction. The ω‐formylpolydienes were characterized by hydroxylamine end‐group titration, FTIR, and both ¹H‐ and ¹³C‐NMR spectroscopy. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1143–1156, 1999     

Synthesis and characterization of a novel Brönsted acidic dicationic ionic liquid based on piperazine and its application in the one-pot synthesis of various xanthenes under solvent-free conditions

In this paper, an interesting Brönsted acidic dicationic ionic liquid based on piperazine was prepared via two-step synthesis. The structure of the dicationic ionic liquid (DIL) was confirmed with various techniques including Fourier transform infrared spectroscopy (FT-IR), Proton NMR (¹H NMR), Carbon-13 NMR (¹³C NMR), mass spectroscopy (MS), acid–base titration as well as Hammett acidity function. Catalytic activity of this novel Brönsted acidic DIL was examined in the xanthene synthesis. High yield of product, short reaction time, easily recovery and reusing of the catalyst, and the absence of organic solvents are some of the merits of the developed procedure.

     

Vergleich dreier komplexometrischer aluminiumbestimmungsmethoden

The complexometric methods for determination of aluminium of Wännien and Ringbom, P?ibil and Sajo are compared. That of P?ibil has a relative error of — 0.3% and a variance of 0.7% in the region of 2.5 mg Al and is preferable. The salt error for sodium acetate, urotropin, sodium chloride, nitrate and sulfate has been studied for the titration with xylenol orange as indicator (P?ibil). The rate of formation of the aluminium complex in strongly acidic medium has been studied in relation to the boiling time.     

Determination of Inorganic and Organic Thiophosphates with Ion-Selective Membrane Electrodes

Abstract

The conditions for the determination of sodium thiophosphate and sodium S-(2-amino-ethyl)-thiophos-phate in the presence of phosphate ion using ion-selective membrane electrodes are described. Both thiophosphates (inorganic and organic) are hydrolyzed in acidic medium. The phosphate ion is determined with Pb(II) using a Pb²⁺ – selective membrane electrode.

Cysteamine is determined by potentiometric titration with Hg(I1) using a Ag⁺/S^2? – crystal membrane electrode or by direct potentiometry with a Cu²⁺ selective membrane electrode. The results were verified by the iodination method.     

Molecular solvent effect on the acidity constant of protic ionic liquids

In this work how the microscopic properties of a molecular solvent affect the chemical environment of the protic ionic liquids (PILs) was analyzed. Using Reichardt’s dye as indicator of acidity, new acidity constant values for eight PILs (pK_a^PILs) were determined by spectrophotometric titration. Modifying the character hydrogen bonding donor of the molecular solvent it is possible to handle the PIL acid strength. Thus, we can turn basic PILs into acidic ones thereby the molecular solvent could be used as ‘additive’ for PILs, which allowed us to tune PILs design.     

Microanalytical Determination of Formaldehyde by Direct Titration with Hydroxylamine Using Interdigitated Microelectrode Array Biamperometric End-Point Indicator

 An interdigitated microelectrode array (IDA) biamperometric titration is presented for the microdetermination of formaldehyde. It is based on a direct titration of formaldehyde with hydroxylamine under the formation of formaldoxime. The released hydrogen cations react with hydroxyl anions in 0.1 M NaOH. The interdigitated pair of two individually polarizable microelectrodes serves as a biamperometric end-point indicator. Hydroxylamine together with dissolved free oxygen behave as a quasi reversible mixed redox system, therefore a significant increase of current flowing between the IDA segments polarized by 100 mV is observed when the first excess of titrant appears in the titrated solution. Because of the small dimension of the IDA sensor this principle can be extended for a microanalytical variant of this method. Formaldehyde contents down to 10⁻³ M in small volume waste water samples could be determined by this technique. These samples usually contain carboxylic acids which interfere in iodimetric determinations, but do not influence the titration of formaldehyde with hydroxylamine. Received January 21, 2002; accepted August 7, 2002     

Analysis of the oxidation of cellulose fibres by titration and XPS

The purpose of this study was to evaluate the effect of selective oxidation on the surface properties of cotton cellulose fibres. Four different methods to evaluate the accessibility, nature and content of ionisable acidic groups (charge) in the fibres were applied: potentiometric and conductometric titrations, polyelectrolyte adsorption and X-ray photoelectron spectroscopy (XPS). The results from this combination of methods show that two processes take place when the oxidation method is applied: elimination of low molecular mass non-cellulosic compounds and formation of new acidic groups in the cellulose chains. Which of these processes is predominating depends on oxidation time, but the first one is initially more important. Polyelectrolyte adsorption and XPS show that the surface concentration of acidic groups is considerably lower than the bulk concentration, i.e. during oxidation the content of carboxyl groups in the surface region decreases, while it increases in amorphous regions. The decrease is due to the dissolution of low molecular weight compounds; the increase is due to the formation of new acidic groups. The use of titration methods in combination with XPS appears to be a very useful tool for identification of the formation and distribution of ionic groups in cotton fibres and their surfaces.     

An Easy Process to Prepare a Copper(I)/Copper Sulfide Electrode and Its Behavior in Alkalimetric Titrations

Abstract

A copper sulfate (Cu₂S) film is formed on the surface of a copper wire by immersion in melted (>55°C) sodium thiosulfate, Na₂S₂O₃·5H₂O. This Cu₂S/Cu electrode is sensitive to sulfide ions and can be used in potentiometric titration of Na₂S solutions with copper(II) cations. Besides, as a novelty, it gives a good response to H⁺ cations at a wide pH range, even in alkaline medium, as checked in potentiometric titration of acetic and phosphoric acids. An analysis of a number of potentiometric measurements leads to interpretation of the electrode response in acidic/basic medium.     

Determination of hexafluoropropan-2,2-diol in its binary mixtures with water

A visual titration method for the determination of hexafluoropropan-2,2-diol (HFPD) in HFPD-water mixtures is suggested. The procedure involves the titration of the weakly acidic HFPD with sodium methoxide, using dimethylformamide or ethanol as solvent and thymol blue as indicator. The results are in good agreement with the ones obtained by potentiometric titration in water.     

Brazilin Inhibits Prostatic Acidic Phosphatase Fibrillogenesis and Decreases its Cytotoxicity

A 39‐amino acid peptide fragment that is derived from prostatic acidic phosphatase (PAP), PAP_248–286, is secreted in large amounts in human semen and forms amyloid fibrils. These fibrils can capture HIV virions and increase the attachment of virions to target cells; as such, they are called a “semen‐derived enhancer of virus infection” (SEVI). Therefore, the inhibition of the formation of PAP_248–286 amyloid fibrils is of great significance. Herein, we demonstrate that brazilin effectively inhibits PAP_248–286 aggregation. The inhibitory effect increases with increasing brazilin concentration. Thioflavin T fluorescence assays and TEM observations confirmed that a few fibrils formed when brazilin was present with PAP_248–286 in an equimolar concentration. Circular dichroism spectroscopy indicated that brazilin inhibited the secondary structural transitions from α‐helices and random coils into β‐sheets. Cytotoxicity assays showed that brazilin significantly decreased the cytotoxicity of the fibrils at 0.01 mmol L⁻¹. Isothermal titration calorimetry revealed that hydrophobic interactions were the main driving force for the binding of brazilin to the PAP_248–286 monomer (dissociation constant, 4.03 μmol L⁻¹), and that the binding affinity of brazilin for the fibrils was at least three orders of magnitude lower than that for the monomer. These results indicate that brazilin holds great potential as a small‐molecule agent against SEVIs.