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By Charles Tanford

Hardcover - December, 1961

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Extra resources for Physical Chemistry of Macromolecules

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6. With decreasing analyte concentration, iF becomes smaller until ( for the case of a 4 s drop time) when if < 2 ic it becomes no longer visually detectable. Note that the small amounts of oxygen and any trace impurities that may be present in the cell solution will not be noticed because their combined faradaic currents are smaller than i,. The iF : i, signal- to- noise r a tio is the determining factor for the sensitivity ofDCP. If more sensitive polarographic determinations are to be performed, this ratio must be increased by using electrical circuitry or techniques in which either the faradaic signal is enhanced or the charging current is minimised or where both can be achieved.

1 4 is small e n o u gh to be n egl ec te d so that E 'l/2 may be i de nt i fi ed with the st an dard po te nt ial for the electr o d e reaction, J::"'ox/ red· Equ a t i o n 2. 1 3 no w b ecom es : . half-wave po te n t i al is . ( 2 . 1 5a) , which is often called the Heyrovsky-Ilkovic equation [ 8 ] . t = E llz r 0 . 0592 + -n- l o g { ( id - i ) --i- } ( 2. 1 5b) When the cell solution contain s b oth the oxidised and reduced forms of the analyte, that is both ( calox > 0 and ( c. l red > 0, th en equation 2.

Q, toward the end of the step as shown in Figure 2. 1 5 [ 1 2 ] . The current, in I ' inz• is measured over a number of cycles, n, twice in each cycle for a short period, tm P t012, just prior to each polarity change of the square-wave voltage cycle. The average of the differences between in1 and i112 for each measurement cycle: = 42 Introduction to Voltammetric Analysis I A o Ill G) li G) u 1 I I _. I tm 1 +- a.. 0 ... G) 0 E I 1 _. I Meas u ring point 1 Drop life I 1 +I t E b Sqm c Figure 2 .

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