Abstract
pH and conductometric study of aqueous (0.1 ÷ 9.0)⋅10-3 mol/l solutions of sodium (Na3Cit), monoethanolammonium (H3Cit⋅3MEA) and polyethylenepolyammonium (kH3Cit⋅3PEPA) citrates was carried out. Features of the electrochemical behavior of monoethanolamine and polyethylenepolamine ammonium citrates aqueous solutions were revealed in comparison with Na3Cit. As the temperature increases from 293 to 303 K, the pH values and Na3Cit solutions molar electrical conductivity increase. Due to hydrolytic processes, when diluting H3Cit⋅3MEA solutions, a change in pH is observed from slightly acidic to slightly alkaline, in contrast to Na3Cit. An increase in temperature (in the region of 293–308 K) leads to an increase in the medium acidity, in contrast to sodium citrate solutions, which is accompanied by an atypical decrease in molar electrical conductivity at the same H3Cit⋅3MEA content. It has been shown that an increase in temperature in the range of 293-308 K leads to a decrease in H3Cit⋅3MEA aqueous solutions pH, in contrast to Na3Cit and kH3Cit⋅3PEPA solutions, which is accompanied by an atypical decrease in molar electrical conductivity at the same H3Cit⋅3MEA content. The component composition of Na3Cit, H3Cit⋅3MEA and kH3Cit⋅3PEPA aqueous solutions was calculated. The probability of the existence of negatively charged ion-molecular complexes in H3Cit⋅3MEA and kH3Cit⋅3PEPA aqueous solutions is shown. The concentration and temperature dependence of citrate ions hydrolysis constant was obtained. The concentration and temperature dependence of these complexes was assessed. The atypical negative effect of heating on H3Cit⋅3MEA aqueous solutions molar electrical conductivity is associated with a change in the radius of the ion-molecular complex and its stability. The value of the limiting molar electrical conductivity of sodium, monoethanolammonium and polyethylenepolyammonium citrates aqueous solutions in the range of 293–313 K was estimated. Correlations were revealed between the values of the limiting electrical conductivity and ion-molecular complexes formation constants in H3Cit⋅PEPA aqueous solutions. The values of energy, enthalpy and entropy of activation of molar electrical conductivities of aqueous solutions were calculated. For the solutions studied, compensation effects were noted in the activation parameters of molar electrical conductivity.
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