Titrimetric determination of fluoride in some pharmaceutical products used for fluoridation.

Two titrimetric methods were developed for the determination of fluoride contents in some pharmaceutical preparations used for fluoridation. One of the methods is catalytic controlled-current potentiometry involving two identical platinum indicator electrodes and thorium nitrate as titrant. The reaction between hydrogen peroxide and potassium iodide in the presence of acetate buffer (pH 3.6), which is catalysed by the excess of thorium nitrate, served for the end-point indication. The other method is the automatic potentiometric titration involving a fluoride-selective electrode and lanthanum nitrate as titrating agent. In both procedures, special attention was paid to sample pretreatment and to determination of optimal experimental conditions. Fluoride contents in the range 16-32 microg/ml are determined with a relative standard deviation less than 1.34%. The results are compared to those obtained by standard methods described in the United States Pharmacopeia XXI and recommended by the manufacturer of the preparations.

Contributions to the theory of catalytic titrations-II Precipitation and redox catalytic titrations.

Precipitation and redox catalytic titration curves, obtained by both volumetric and coulometric addition of the titrant, have been simulated, taking into account the equilibrium concentration of the catalyst during the titration. The influence of several factors on the shape of the simulated catalytic titration curves has been investigated and is discussed in detail. Simulations of the blank titrations have also been made.

Contributions to the theory of catalytic titrations-III Neutralization catalytic titrations.

Neutralization catalytic titrations of weak monoprotic adds and bases with both volumetric and coulometric addition of the titrant (strong base/acid) have been simulated by taking into account the equilibrium concentration of the catalyst during the titration. The influence of several factors on the shape of the simulated catalytic titration curve has been investigated and is discussed.

Contributions to the theory of catalytic titrations--I: Complexometric catalytic titrations.

Complexometric catalytic titrations with both volumetric and coulometric addition of the titrant have been simulated. By taking into consideration the equilibrium concentration of the catalyst during the titration, general mathematical equations have been set up. The influence of several factors on the shape of the simulated catalytic titration curve has been investigated and is discussed. The work also deals with the conditions under which the approximate mathematical expressions (equilibrium concentration of the catalyst being neglected) can be applied to simulate the catalytic titration curves with a satisfactory accuracy.

Catalytic amperometric and catalytic constant-current potentiometric titrations of silver(I), palladium(II) and mercury(II).

Amperometry and constant-current potentiometry were used to follow the course of catalytic titrations of silver(I), palladium(II), and mercury(II) with potassium iodide. The Ce(IV)As(III) and Ce(IV)Sb(III) systems in the presence of sulphuric acid were used as indicator reactions. The possibilities of application of platinum, palladium, gold, graphite, and glassy-carbon indicator electrodes were investigated. Graphite appeared to be somewhat more advantageous than the other electrode materials. The effect of concentration of the components of the indicator reactions, the presence of organic solvents and acids on the shape of the catalytic titration curves was studied. Amounts of 30-3000 mug of silver(I) nitrate, 90-900 mug of palladium(II) chloride, 130-1300 mug of mercury(II) chloride, and 150-1500 mug of mercury(II) nitrate were determined with a relative standard deviation less than 1.0%. The results obtained were in good agreement with those of comparable methods. The catalytic titration method developed was applied to determination of mercury in Unguentum Hydrargyri.

Determination of fluoride with thorium nitrate by catalytic titration.

Amperometry, constant-current potentiometry and spectrophotometry were used to follow the course of catalytic titrations of fluoride and silicofluoride with thorium nitrate. The hydrogen peroxide-iodide system was used as the indicator reaction. Titrations were performed in 50% ethanolic acetate buffer, pH 3.6. Amounts of 3.70-6.85 mg of ammonium fluoride, 5.53-10.79 mg of potassium fluoride and 4.34-8.41 mg of sodium silicofluoride were determined with a maximum average deviation of 0.9%. The results obtained are in good agreement with those of comparable methods.

Catalytic thermometric titrations in non-aqueous solvents by coulometrically generated titrant.

Catalytic thermometric titrations have been developed for tertiary amines and salts of organic acids in acetic and propionic anhydride with titrant coulometrically generated at a mercury and/or platinum anode, hydroquinone being added to the solution titrated if the platinum anode is used. The results obtained are compared with those obtained by coulometric titration with the end-point detected either photometrically or potentiometrically. On a élaboré des titrages thermométriques catalytiques pour les amines tertiaires et les sels d'acides organiques en anhydrides aétique et propionique avec l'agent de titrage engendré coulométriquement sur une anode de mercure et/ou platine, de l'hydroquinone étant ajoutée à la solution titrée si l'on emploie l'anode de platine. Les résultats obtenus sont comparés avec ceux obtenus par titrage coulométrique avec le point de fin de réaction détecté soit photométriquement soit potentioétriquement.

Determination of organic bases in non-aqueous solvents by catalytic thermometric titration.

Catalytic thermometric titrations have been developed for bases (brucine, diethylaniline, potassium acetate and triethylamine) in acetic acid by continuous and discontinuous addition of the standard solution and automatic temperature recording. The determination of weak bases, e.g., antipyrine, unsuccessful in acetic acid by catalytic thermometric titration, has been achieved by using nitromethane or acetic anhydride as solvent. Catalytic thermometric titrations were also performed by coulometric generation of hydrogen ions for the determination of micro amounts of weak bases in a mixture of acetic anhyride and acetic acid.

Determination of tertiary amines and salts of organic acids in acetic acid by catalytic thermometric titration.

A new method of determination of tertiary amines and salts of organic adds in acetic acid solution, to which about 2 % of water and 8% acetic anhydride are added, is described. After the equivalence point, the excess of perchloric acid catalyses the exothermic reaction of water with acetic anhydride. The end-point is determined from the graph of temperature against volume of added titrant. If a slightly soluble compound is produced during the titration, the precision of the new method is superior to that of the potentiometric method.