. Ajmaline (AJ) and homatropine (HM) react with bromocresol green (BCG) and bromophenol blue (BPB) in dichloromethane forming 1: 1 and 1:2 ion pairs clearly in a chemical equilibrium. Thermodynamic parameters AGO, AH', and ASQ are calculated using the Van't Hoff equation. In a large excess of HM a product P is formed from the 1:2 ion pair in a pseudo-first order kinetic process which fits Arrhenius' equation. The P product has been identified as a type of charge transfer complex. The thermodynamic parameters corresponding to the formation of the ion pairs BPB-(AJ), , BCG-(AJ),, BPB-(HM), , and BCG-(HM), are, respectively: AGO at 294 K, -26, -21, -26, and -19 kJ/mol; AH O, -63, -39, -63, and -61 kJ/mol; AS', -125, -62, -125, and -138 J/K mol (AH' and AS0 determined in a 288 to 3 13 K range). The values of the activation energy, E,, for the reaction of HM (in large excess) with BCG and BPB are 58 and 91 kJ/mol.
IntroductionThe two phase photometric titration of amines with sulphonphthaleinic dyes is an important method for the analysis of pharmacologically active substances.The most widely proposed dye is bromothymol blue (BTB) because of its high hydrophobicity and exclusive extraction as 1:l associates in the complete pH range (1-6).The reaction, however, is unspecific. This is a disadvantage and a number of studies have been dedicated to this aspect (7,8). More recently, Sakai (9, 10) has proposed a method of selective extraction for a number of quaternary ammonium ions using the 1:2 associates of bromocresol green (BCG) and bromophenol blue (BPB) and quinine as a favourable substance for quantitative extraction of the complex. The stoichiometry assigned to the complex is 1: 1: 1 (quinine:dye:ammonium ion) and it is the quinine which is responsible for the specificity of the extraction of the'quaternary ammonium ion. The dye is extracted as divalent anion, X2-, associated at the same time with protonated quinine, QH+, and the quaternary ammonium compound, B' .In this study the formation of ion pairs of the divalent anion, X2-, of BCG and BPB with the alkaloids ajmaline (AJ) and homatropine (HM) is investigated. The changes in the visibleultraviolet absorption spectra of mixed solutions of BCG and BPB with variable quantities of AJ and HM in dichloromethane are elucidated. The formation of 1: 1 and 1:2 ion pairs in a clear chemical equilibrium is established and the variations in the thermodynamic variables, AGO, AH', and AS' are calculated from the spectrophotometric measurements.With a large excess of HM there appear new changes in the visible absorption spectrum of BCG and BPB; changes which cannot be attributed to the formation of ion pairs. The formation of a third product, P, in a pseudo-first order kinetic process is established, and the kinetic parameters are calculated from the spectrophotometric measurements.