Theoretical and experimental investigation have been made on a method
called the second reciprocal derivative constant-current stripping ana
lysis (SRD-CCSA). The SRD-CCSA is based on the measurement of the d(2)
t/dE(2) signal given by the curve of (d(2)t/dE(2)) versus the electrod
e potential (E). The d(2)t/dE(2)-E curve gives a maximum value (d(2)t/
dE(2))(max) and a maximum value (d(2)t/dE(2))(min), which show as two
peaks on the curve. Either of the heights of the peaks and the sum of
absolute values of the two peaks are proportional to the bulk concentr
ation of the analyte in solution, and they are much larger than (dt/dE
)(p) in the first reciprocal derivative constant-current stripping ana
lysis (FRD-CCSA). The ratio of peak-peak height in the SRD-CCSA to pea
k height in the FRD-CCSA is about 43n (where n represents the number o
f electrons transferred during the electrode process for the analyte).
Potential difference (W-pp) between the two peaks is 48.2 mV n(-1) at
25 degrees C in the SRD-CCSA, which is noticeably smaller than the ha
lf-height width W-p/2 65.5 mv n(-1), in the FRD-CCSA. The theory was v
erified with a home-made multireciprocal derivative measuring instrume
nt. The experimental results were in good agreement with the theoretic
al ones.