Amidoximes are compounds bearing both hydroximino and amino functionality at the same carbon atom, and are thus closely associated with amides, amidines and hydroxamic acids. These compounds are of great importance for the synthesis of various heterocycles. The complex formation capability of amidoximes makes use of the determination of Cu, Hg, Pb, and group 8, 9 and 10 metals. Among the coordination compounds, those with Mo and W central atoms are the most important. Amidoximes have found numerous technological applications, such as corrosion inhibition, stabilizing polymers and paper strengthening. Amidoxime functionalized polymeric coatings are being developed for chemical electronic microsensors. Another important application of amidoximes is uranium recovery from seawater. Amidoximes, especially those carrying arylsulfonyl and pyridyl groups, were reported to have shown significant biological activities, like hypoglycaemic, analgesics, pesticides, herbicides, and antihypertensic. 1 To the best of our knowledge, there has been no report concerning the determination of the protonation constants of Nsubstituted amidoximes. Upon contiuning our studies on the determination of the protonation constants, 2,3 in this study we considered the protonation constants of some N-substituted amidoximes in 50% ethanol-water mixtures (v/v). Since these compounds sparingly dissolve in water, an ethanol-water mixture was used as a medium in titrations. The stoichiometric protonation constants were measured by a potentiometric titration method and calculations were carried out using PKAS computer software. 4 The structures and protonation constant values of the compounds under investigation are given in Table 1.
ExperimentalAll of the compounds studied were synthesized as described previously 5,6 and checked chromatographically for purity. Stock solutions of these compunds were prepared in purified ethanol. 7 The standard amidoxime solutions were prepared in 50% aqueous ethanol. A 0.1 M perchloric acid solution was prepared in water and standardized by titration against primary standard sodium carbonate. Double-distilled deionized water was used throughout the experiments.Chemically pure sodium perchloride was used to maintain a constant ionic strength. Sodium chloride and sodium perchloride were purchased from Merck and used as received. An alkali solution containing 0.1 M NaClO4 was prepared using NaOH (Merck) in 50% ethanol-water mixture and standardized potentiometrically against a perchloric acid solution using Gran's plot techniques, allowing a determination of the dissolved carbonate impurity. 8,9 Potentiometric titrations were performed in a 80-mL glass vessel equipped with a combined pH electrode (Ingold), nitrogen inlet and outlet tubes, a magnetic stirrer and a titrant inlet. The electrode was modified by substituting its aqueous potassium chloride solution for a mixture of 0.01 M NaCl + 0.09 M NaClO4 saturated with AgCl. An Orion Model 720A pH ionmeter was used to measure the cell e.m.f. (the uncertainity of e.m.f. ...