p-Aminobenzoate ion determination in pharmaceutical formulations by using a potentiometric sensor immobilized in a graphite matrix.

The characteristics, performance, and application of an electrode, namely, Pt|Hg|Hg(2)(PABzt)(2)| graphite, where PABzt stands for p-aminobenzoate ion, are described. This electrode responds to PABzt with sensivity of (58.1+/-1.0) mV per decade over the range 1.0x10(-4) to 1.0x10(-1)moll(-1) at pH 6.5-8.0 and a detection limit of 3.2x10(-5)moll(-1). The electrode shows easy construction, fast response time (within 10-30s), low-cost, and excellent response stability (lifetime greater than 6 months, in continuous use). The proposed sensor displayed good selectivity for p-aminobenzoate in the presence of several substances, especially, concerning carboxylate and inorganic anions. It was used to determine p-aminobenzoate in pharmaceutical formulations by means of the standard additions method. The results obtained by using this electrode compared very favorably with those given by an HPLC procedure.

Chromotropic acid-formaldehyde reaction in strongly acidic media. The role of dissolved oxygen and replacement of concentrated sulphuric acid.

The procedure for formaldehyde analysis recommended by the National Institute for Occupational Safety and Health (NIOSH) is the Chromotropic acid spectrophotometric method, which is the one that uses concentrated sulphuric acid. In the present study the oxidation step associated with the aforementioned method for formaldehyde determination was investigated. Experimental evidence has been obtained indicating that when concentrated H(2)SO(4) (18 mol l(-1)) is used (as in the NIOSH procedure) that acid is the oxidizing agent. On the other hand, oxidation through dissolved oxygen takes place when concentrated H(2)SO(4) is replaced by concentrated hydrochloric (12 mol l(-1)) and phosphoric (14.7 mol l(-1)) acids as well as by diluted H(2)SO(4) (9.4 mol l(-1)). Based on investigations concerning the oxidation step, a modified procedure was devised, in which the use of the potentially hazardous and corrosive concentrated H(2)SO(4) was eliminated and advantageously replaced by a less harmful mixture of HCl and H(2)O(2).

Ionic medium effects on equilibrium constants Part I. Proton, copper(II), cadmium(II), lead(II) and acetate activity coefficients in aqueous solution.

The molar single ion activity coefficients associated with hydrogen, copper(II), cadmium(II) and lead(II) ions were determined at 25 degrees C and ionic strengths between 0.100 and 3.00 M (NaClO4), whereas for acetate the ionic strengths were fixed between 0.300 and 2.00 M, held with the same inert electrolyte. The investigation was carried out potentiometrically by using proton-sensitive glass, copper, cadmium and lead ion-selective electrodes and a second-class Hg|Hg2(CH3COO)2 electrode. It was found that the activity coefficients of these ions (y(i)) can be assessed through the following empirical equations: log y(H) = -0.542I(0.5) + 0.451I; log y(Cu) = -1.249I(0.5) + 0.912I; log y(Cd) = -0.829I(0.5) + 0.448I(1.5); log y(Pb) = -0.404I(0.5) + 0.117I(2); and log y(Ac) = 0.0370I

Ionic medium effects on equilibrium constants Part II. Binary systems comprising some bivalent cations and monocarboxylates in aqueous solution.

Simple equations were derived relating stoichiometric protonation constants of several monocarboxylates and formation constants associated with 1:1 complexes involving some bivalent cations and selected monocarboxylates, in aqueous sodium perchlorate media, at 25 degrees C, as a function of ionic strength (I), allowing the interconversion of parameters from one ionic strength to another, up to I=3.00 M. In addition, thermodynamic formation constants as well as activity coefficients of the species involved in the equilibria were estimated. The results show that the proposed calculation procedure is very consistent with critically selected experimental data.

Determination of cinnamic acid in human urine by differential-pulse polarography.

The differential-pulse polarographic behaviour of cinnamic acid was studied in acetate and phosphate buffer solutions (pH 3.5-7.5). The reduction mechanism is discussed. The drug can be determined at pH 5.0 over the concentration range 5 x 10(-5)-1 x 10(-3) mol l-1. The effect of tetraalkylammonium salts on the electroanalytical determination of cinnamic acid was investigated. The direct determination of the drug (0.7-5.5 micrograms ml-1) in urine samples diluted with acetate buffer (pH 5.0) can be effected in the presence of 1 x 10(-3) mol l-1 cetyldimethylethylammonium bromide solution. The detection limit was found to be 0.1 microgram ml-1. The relative standard deviation from six determinations at the 5.5 micrograms ml-1 level was 1%.