3-methyl-2-oxazolidone as a solvent for acid-base titrations

3-Methyl-2-oxazolidone has been evaluated as a solvent for the titration of various weak carboxylic acids and phenols. Its high dielectric constant and wide liquid range contribute to its outstanding solvent properties. Tetrabutylammonium hydroxide was the titrant. End-points were determined potentiometrically with a glass-calomel electrode system. FORTRAN computer programs were used to evaluate the results, and relative acid strengths were determined and related to the aqueous acidity. The accuracies obtained are comparable to those for other solvent media. An 800-mV potential span is available in this solvent, which may allow differentiating titrations to be performed. No titrations of acid mixtures were attempted, but it was found possible to distinguish both neutralization steps for salicylic acid and o-phthalic acid.     

A conductometric method for colloid titrations

A negative or positive colloid sample solution can be directly titrated, respectively, with a polycationic (poly-N, N-diallyldimethylammonium chloride) or polyanionic (potassium polyvinylsulfate) titrant to a conductometric end-point. With the conventional toluidine blue indicator method a positive colloid solution is titrated directly with a polyanionic titrant, but a negative colloid solution must be treated with an excess of a polycationic titrant, which is back-titrated with the polyanionic titrant. For positive colloid solutions, both indicator and conductometric methods are suitable; for negative colloids the conductometric method is preferable because of its constant titration vlues over a range of pH values.     

Some observations on catalytic conductometric titrations

Conductometric and high-frequency conductometric methods for the determination of the endpoint of catalytic titrations were developed. Titrations of sodium acetate were made in a mixture of acetic anhydride and acetic acid (7:3–11:3) which was 0.05–0.1 mol dm⁻³ in sodium perchlorate. Integral and derivative titration curves were recorded in both coulometric and volumetric titrations. Different acylation reactions, as well as dehydration of formic acid, were used as the indicator reactions. The optimal conditions of determination—choice of volume ratio of acetic anhydride to acetic acid, rate of the titrating reagent addition, concentration of sodium perchlorate, and concentration of several alcohols, water, and formic acid as components of the indicator reactions—were determined. Using the catalytic conductometric method, amounts of 0.04–11 mg of sodium acetate were determined with a relative standard deviation of less than 0.8 and 1.6% in volumetric and coulometric addition, respectively. Using the catalytic high-frequency conductometric method, amounts of 1–11 mg of sodium acetate were determined with relative standard deviation less than 0.5% (volumetrically) or less than 1.4% (coulometrically). The obtained results were compared with those of potentiometric and catalytic thermometric titrations.     

Radiometric acid-base titrations

Acid-base titrations can be performed with radiometric end-point detection by use of labelled metal salts (e.g., ZnCl(2), HgCl(2)). Owing to the formation or dissolution of the corresponding hydroxide after the equivalence point, the activity of the titrated solution linearly increases or decreases as excess of standard solution is added. The end-point of the titration is determined graphically.     

The use of 2,6-dichlorophenolindophenol as indicator in acid-base titrations

2,6-Dichlorophenolindophenol shows acid-base indicator properties. Its colour is red in acidicmedia and blue in alkaline media. 'Ihe transitional pH value is 5.7 and the colour change is sharp and easy to observe. The use of the indicator in various acid-base titrations, as well as the effects of neutral salts, alcohol and temperatures, were checked. The absorption spectra of the acidic and basic forms of the indicator are presented.     

High precision automated conductometric titrations with the bipolar pulse technique

An automated conductometric titration system has been designed and investigated. Stepper motor driven burets have been constructed to provide precise delivery of small volumes of titrant. A bipolar pulse conductance instrument of wide dynamic range is briefly reviewed as a tool in conductometric titrations. Several types of titrations have been carried out to investigate the accuracy and reproducibility of this apparatus. The precision for titrant volumes of 40µl is ±0.64% relative standard deviation.     

Calculated equivalence volume in potentiometric acid-base titrations

Summary Using a pH meter, a motorized burette and a programmable pocket calculator potentiometric acidbase titrations may be carried out with a high degree of precision, a high degree of accuracy and in a time comparable to the time needed to perform a titration with a visual indicator. With the exception of the lowest concentration of the weak acid a precision higher than 0.01 ml of the reagens is easily obtainable, whereas the accuracy may be as high as 0.1 %. The method is suitable over a wide range of concentrations of either strong or weak acids.

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Berechnetes Äquivalenzvolumen bei potentiometrischen Säure-Base-Titrationen

Zusammenfassung Mit Hilfe eines pH-Meßgeräts, einer Motorbürette und einem programmierbaren Taschenrechner können potentiometrische Säure-Base-Titrationen mit hoher Reproduzierbarkeit und Richtigkeit in einer mit der Verwendung von visuellen Indicatoren vergleichbaren Zeit durchgeführt werden. Mit Ausnahme der niedrigsten Konzentration einer schwachen Säure wurde eine Reproduzierbarkeit von besser als 0,01 ml und eine Richtigkeit von 0,1 % erhalten. Das Verfahren ist für einen weiten Konzentrationsbereich von starken und schwachen Säuren geeignet.

     

The aluminium indicator electrode in acid-base potentiometric titrations

Aluminium has been employed as an indicator electrode in potentiometric acid-base titrations. The titration curves obtained were approximately 3.6 times broader than those obtained with the antimony electrode.     

Evaluation of potentiometric acid-base titrations by partial-least-squares calibration

Partial-least-squares calibration is used for the evaluation of acid-base titration curves. The method is advantageous because no physical model is assumed and only information from the titration curves is used. In the procedure, a model is developed from samples of known composition (calibration set) and is then used to predict unknowns (test set). The only assumption is that the two sets are similar. The method was evaluated first by titrating mixtures of two monoprotic acids with a small difference in pK_a values and then by titrating samples containing four or five diprotic acids. The results show that it is possible to determine monoprotic acids having a difference in pK_a of only 0.1, or up to five diprotic acids having pK_a values in the range 1.8–7.2, simultaneously.     

A twinned mercury-filled glass electrode system for acid-base titrations in a number of non-aqueous solvents

A pair of mercury-filled glass electrodes is proposed for acid-base titrations in non-aqueous solvents or their mixtures with each other or with water.     

Calorimetric and conductometric titrations of nanostructures of water molecules in iteratively filtered water

This work continue the study of the physico-chemical properties of samples of pure, twice distilled water, when subject to a procedure of iterative filtrations through Pyrex glass filters (Büchner funnels). After the filtrations, electrical conductivity and heat of mixing with NaOH and HCl solutions increase. The hypothesis is that the iterative filtration procedure, that involves a flux of energy and material in an open system, is able to induce the formation of “dissipative structures” or nanostructures of water molecules (WNS). Water exhibits an extraordinary auto-organization potentiality triggered by several kinds of perturbations, including mechanical ones. We measured the heats of mixing of acid or basic solutions with such iterated filtered waters (IFW) and their electrical conductivity, comparing with the analogous heats of mixing, electrical conductivity of the solvent. We found some relevant exothermic excess heats of mixing and higher conductivity than those of the untreated solvent. The heats of mixing and electrical conductivity of IFW show a good correlation, underlining a single cause for the behavior of the samples.     

Eriochrome black a as an indicator for chelatometric titrations

The use of Eriochrome Black A for the EDTA titrations of Zn, Mn, Ni, Pb and Cu ions is described. Spot tests for the determination of the sensitivity limits of detection have been made     

Logarithmic diagrams in acid-base titrations and estimation of titration errors

The use of a logarithmic diagram for the estimation of the pH-value at the equivalence point and the titration error when a solution containing one or two acids is titrated with standard alkali is described.     

Microemulsions with CO2 as a solvent

Supercritical CO₂ is considered as a promising alternative for volatile organic solvents currently used in certain industrial processes and products, however, the poor solubilizing power of CO₂ towards polar substances remains a significant barrier to applications. Employing effective surfactants which generate stable dispersions and water/CO₂ microemulsions is accepted as one way to improve the physico-chemical properties of CO₂. This article reviews recent studies on microemulsions in liquid CO₂, as well as the development of CO₂-philic surfactants.     

Dehydration-dehydrogenation of 2-propanol as a model reaction for acid-base characterization of catalysts

The relationship between the acid-base properties of various solids, as determined by a spectrophotometric procedure and the apparent dehydrogenation (K₁) and dehydration rate constant (K₂) of 2-propanol have been studied by using a continuous-flow reactor.     

Solubility of Tris-(hydroxymethyl)-aminomethane in water-2-methoxyethanol solvent mixtures and the solvent effect on the dissociation of the protonated base

Solvent effects are discussed in terms of the free energies of transfer G_t ⁰ from water to aqueous 2-methoxyethanol (MCS) solvents, of the uncharged base (B) evaluated from the measured solubilities, of HCl evaluated earlier, and of Tris hydrochloride (B.HCl). The characteristic minimum at 25°C is attributed to selective solvation of the individual species involved in the equilibrium process. The results indicate that the primary solvation either of H⁺ or BH⁺ ions arising from specific ion-dipole interactions outweigh the electrostatic or the secondary solvation effect.     

Electrogenerated iodine as a reagent for coulometric titrations in alcoholic media

Conditins are established for the generation of iodine with high current efficiency (>99%) in solutions of potassium acetate in methanol or ethanol, in the presence of potassium iodide or tetraethylammonium iodide at platinum or glassy carbon working electrodes, respectively. Iodine solutions in methanol are stable, but solutions in ethanol are less so. Procedures are given for coulometric titration of various thiols with anodically generated iodine in these solvents; biamperometric or potentiometric end-point detection can be used. The error of the titrations did not exceed ± 2.0% for ca. 1-mg samples.     

Thermometric titrations of amines with nitrosyl perchlorate in acetonitrile solvent

Thirteen aliphatic and four aromatic amines, namely diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-butylamine, isopropylamine, di-isopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, aniline, N,N-dimethylaniline, 2-nitroaniline and 4-nitroaniline were titrated thermometrically with nitrosyl perchlorate in acetonitrile solvent. All the aliphatic amines gave very well-shaped thermometric titration curves. The calculated recovery values of the amines were very good. In comparison, the aromatic amines, aniline and N,N-dimethylaniline gave rather well-shaped titration curves, but the recovery values were fairly low. 2-Nitro- and 4-nitro anilines gave no thermometric response at all. The heats of reaction of the amines with nitrosyl perchlorate are rather high. However, the average heat of reaction of the aromatic amines is approximately two-thirds that of the average heat of the aliphatic amines. To support this method all the amines were also titrated potentiometrically and very similar results to those obtained with the thermometric method are seen. The nitrosyl ion is a Lewis acid, strong enough to titrate quantitatively aliphatic amines in acetonitrile solvent, but not strong enough to titrate aromatic amines at the required level in the same solvent.     

Luminol as a fluorescent acid-base indicator

The acid and base dissociation constants of luminol are determined at various ionic strengths. The transition interval occurs at pH 7.7-9.0, therefore luminol is a fluorescent indicator for the titration of strong and weak acids and strong bases. Its value as an indicator is established by titrating milk, red wine and cherry juice.