Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 2, pp. 247−254.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
D.O. Kirsanov, O.V. Mednova, E.N. Pol’shin, A.V. Legin, M.Yu. Alyapyshev, I.I. Eliseev, V.A. Babain, Yu.G. Vlasov, 2009, published
in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 2, pp. 254−261.
AND CORROSION PROTECTION OF METALS
New Polymeric Chemical Sensors for Determination of Lead Ions
D. O. Kirsanov, O. V. Mednova, E. N. Pol’shin, A. V. Legin, M. Yu. Alyapyshev, I. I. Eliseev,
V. A. Babain, and Yu. G. Vlasov
St. Petersburg State University, St. Petersburg, Russia
Received January 12, 2009
Abstract—New polymeric electrochemical sensors for determining the content of lead were suggested. As the
active substance of the polymeric membranes of the sensors was used N,N'-tetrabutyldipicolinamide, the compound
exhibiting a high extractive capacity for heavy metal ions. The selectivity of the sensors with respect to lead ions
in the presence of copper, cadmium, and zinc in a considerable excess was studied.
The development of modern methods of analytical
chemistry is aimed in many respects to devise instruments
and approaches that provide fast, accurate, and reliable
chemical analysis of samples in the real-time mode.
Analytical methods of this kind are in high demand both
in the industry, for monitoring of various technological
processes, and in ecological inspection of natural samples.
A particular place among important tasks for chemists-
analysts is occupied by the problem of lead determination.
This circumstance is due both to the wide occurrence of
this element in various technological processes and to its
high toxicity for living organisms.
Various methods exist for determination of lead:
complexonometry, electrogravimetry, spectrophotometry,
and atomic absorption spectrometry. As a rule, most of
these techniques involve complicated and prolonged
sample preparation, large amount of expendable materials,
need to use the labor of highly skilled personnel, and
high-cost the equipment. Apparently, only a limited
number of analytical methods enable automated on-line
measurements. As an attractive instrument satisfying the
requirements of rapidity and reliability of determination,
simplicity of use, and possibility of measurement
automation may serve chemical sensors and, in particular,
ion-selective electrodes (ISEs).
A comparatively large number of various types of
ISEs for determination of lead have been developed.
These include chalcogenide glass electrodes [1, 2], widely
used sensors with polycrystalline sulﬁ de membranes,
and also ISEs with membranes based on various organic
complexing agents. Among these types of ISEs, the last
variety of sensors is the subject of the largest number of
publication, which is due to the apparent advantages of
polymeric materials. ISEs of this kind enable controlled
variation of their electrochemical characteristics via
modification of the chemical structure of the active
substance of the membrane, ionophore, capable of
selective complexation with target ions. In addition, it is
possible to control the sensor properties by varying the
ratio between the membrane components, ionophore, and
ion-exchange additive, and by changing the polarity of
the plasticizer-solvent. In recent years, the researchers’
interest in ﬁ lm-type electrochemical sensors has been
steadily growing, principal theoretical concepts of
operation of such sensors have been revised, it has been
shown that electrodes of this type provide exceedingly low
detection limits, concepts of the selectivity coefﬁ cients
have been reconsidered, and potentiometric techniques
with external current ﬂ ows have been developed [3–5].
A major disadvantage of solid-state PbS ISEs is the
membrane poisoning by Hg
, and Cu
circumstance has initiated a search for new substances-
ionophores for PVC-plasticized membranes. However,
analysis of published data shows that a large number
of polymeric ﬁ lm electrodes for determination of lead
developed by now have the same disadvantages: their
selectivity with respect to lead in the presence of copper
and cadmium ions is, as a rule, low. This circumstance
strongly restricts the variety of the possible practical
applications of sensors of this kind, because lead, copper,