ISSN 0965?5441, Petroleum Chemistry, 2011, Vol. 51, No. 7, pp. 496–505. © Pleiades Publishing, Ltd., 2011.Original Russian Text © O.V. Bobreshova, A.V. Parshina, K.A. Polumestnaya, S.V. Timofeev, 2011, published in Membrany i membrannye tekhnologii, 2011, Vol. 1, No. 1, pp. 27–36.496INTRODUCTIONCurrent studies on potentiometric sensors havebeen performed in the following areas [1]: the searchfor new materials for the development of ion?selectiveelectrodes (ISEs); miniaturization of sensors; elimi?nation of the transmembrane flow of determined ionsfrom the ISE internal reference solution into the testsolution; the development of the ISE theory withoutequilibrium or steady?state limitations; and research?and?development work on multisensor systems foranalysis of multicomponent liquid media.The classical theory of ISEs is based on the Nikol?sky theory of a glass electrode [2]. The Nikolsky–Eisenman equation is used for describing the sensorresponse in multicomponent solutions, and the effectof interfering ions is considered with selectivity con?stants, the use of which is strictly correct only forbinary systems [3].The multisensor system includes an array of cross?sensitive sensors, that is, sensors sensitive to severalcomponents of the analyzed solution, and the algo?rithm of processing multidimensional data from thearray of sensors [3, 4]. In analyzing a multicomponentsolution, the response of the array of cross?sensitivesensors is complex and it contains information on dif?ferent components present in the solution and theirinteractions. The use of multivariate analysis makes itpossible to decrease the uncertainty of analysis and toreveal latent internal relationships between variablesdue to an increase in their number [5]. An adequatedata processing method depends on the analyticalproblem to be solved (recognition, identification,classification, or quantitative analysis) [3, 4]. Mathe?matically and statistically, a multidimensional casecan be described with smaller dimension models bydata decomposition with the use of sections and pro?jections [5]. A calibration model for describing theresponse of a sensor in a multicomponent solution is aplane that passes at an optimum distance (in terms ofthe least squares technique) from all data, which are acloud of points in a multidimensional space [3–5].The use of the Donnan potential in place of themembrane potential as an analytical signal in thedevelopment of potentiometric sensors makes it possi?ble to decrease the effect of migration and diffusion ofions on the analytical signal and thereby increase theaccuracy, stability, selectivity, and sensitivity of analy?sis [6–8]. The dependence of the Donnan potential onthe nature and concentration of organic and inorganicions in solution and ion?exchanger phases makes itpossible to use these sensors as cross?sensitive sensorsA New Type of Potentiometric Sensors Based on Perfluorinated, Sulfonated Cation?Exchange Membranes for Quantitative Analysis of Multicomponent Aqueous SolutionsO. V. Bobreshova a , A. V. Parshina a , K. A. Polumestnaya a , and S. V. Timofeev ba Voronezh State University, Voronezh, Russiab OAO Plastpolimer, St. Petersburg, Russiae?mail: olga1@box.vsi.ruReceived October 4, 2010Abstract —The organization principles of a new type of sensors were developed whose analytical signal is theDonnan potential at the ion?exchange polymer/test solution interface (PD?sensors) for the determination oforganic and inorganic electrolytes in multicomponent aqueous solutions. It was found that the cross sensitiv?ity of PD?sensors based on perfluorinated, sulfonated cation?exchange polymers (PSPs) in the initial inor?ganic forms depends on the potential?determining reactions of protolysis and ion exchange at the PSP/mul?ticomponent test solution interface. The effects of the hydrophilicity, moisture capacity, and ionic form of theion?exchange polymer on PD?sensor sensitivity were investigated. It was found that treatment of PSP withethylene glycol at the glass?transition temperature of the polymer makes it possible to obtain modified PSPsin organic forms, which differ from the initial materials by a larger concentration of dissociated counterions,and thus lead to enhanced PD?sensor response and sensitivity to an appropriate organic component. Poten?tiometric multisensor systems including cross?sensitive PD?sensors, ion?selective electrodes (ISEs), andalgorithms for the processing of multidimensional data for the quantitative determination of lysine,novocaine, lidocaine, thiamine, pyridoxine, nicotinic acid, and alkali and alkaline earth metal cations inmulticomponent solutions were developed.DOI: 10.1134/S0965544111070048
