A new type of investigation into surface
phenomena, "tensammetry", has been developed by superimposing a small
sinusoidal A.C. voltage upon the direct potential applied to a dropping mercury
electrode in the presence of surface active substances and measuring the
resultant A.C. currents. Wave shaped current-voltage curves are thus obtained
which have their origin in adsorption processes occurring at the electrode.
These waves are attributed to the movement of surface active molecules in the
region of "active space" near the electrode without actual electron
transfer across the electrode boundary; that is, the electrode remains
polarized with respect to U.C., but is depolarized with respect to A.C. The
general properties of tensammetric waves of a number of organic compounds
together with their effects on one another and on D.C. and A.C. polarographic
waves have been investigated. The theoretical basis and the fundamental
equations governing the tensammetric, process are derived and discussed.
A method of polarographic analysis
employing the superposition of a small sinusoidal alternating field of low
frequency upon the direct potential applied to the dropping mercury electrode
has been further developed. Equations are given for the calculation of the
ionic concentration from the alternating current (maximum differential current)
at the characteristic " summit potential " (analogous to E+ in
conventional polarography). This current is proportional to the concentration
of the ion species undergoing discharge. The advantages of the method over
conventional polarography can be summarized as follows :
(i) A.C.
polarography can be carried out in solutions containing dissolved oxygen, i.e.
in air.
(ii) Tedious curve plotting is substituted
by a single current reading at the summit potential which yields directly both
the half-wave potential and the concentration of the electro-reducible
substance. �� (iii) Small amounts of less noble ions can
be estimated even in the presence of a large excess of nobler ions.
(iv) Polarographic waves only 40 mV. apart
are clearly separable.
(v) An improved all round reproducibility
is obtained.
(vi) There is a simplified system of
recalibration in case of capillary replacement.
vii) The use of a delicate galvanometer is
eliminated.
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