Aasc. Machado et al., MULTIWAVELENGTH ANALYSIS OF SYNCHRONOUS FLUORESCENCE-SPECTRA OF THE COMPLEXES BETWEEN A SOIL FULVIC-ACID AND CU(II), Analytica chimica acta, 292(1-2), 1994, pp. 121-132
The variations observed in the synchronous fluorescence spectra of a s
oil fulvic acid, collected in the north of Portugal, with pH (between
2 and 7) and with Cu(II) concentration (at pH 3, 4, 5 and 6 and total
copper concentrations between 0.005 and 4 mM depending on the pH) were
studied by SIMPLISMA, a self-modelling mixture analysis technique. Th
ree components were deeected when varying the pH, corresponding to thr
ee acid-base equilibria with pK(a) values around 3.0, 5.0 and 6.0, and
their individual spectra were obtained. Two components were detected
when varying the Cu(II) concentration, corresponding to two different
ligand sites, and their spectra and concentration profiles (based on t
he two detected pure variables) were obtained. The spectrum of one bin
ding site is similar to the component associated with the acid-base eq
uilibrium with pK(a) = 3.0 and that of the other binding site is simil
ar to the sum of the spectra of the components associated with the oth
er two acid-base equilibria. Using a 1:1 stoichiometry for complex for
mation, complexation capacities (C-L) and stability constants (K) were
calculated for the two binding sites at the four pH values. The calcu
lated stability constants were log K-1 = 3.42(4), log K-2 = 3.05(5) at
pH 3, log K-1 = 4.17(3), log K-2 = 3.71(1) at pH 4, log K-1 = 4.51(3)
, log K-2 = 3.95(2) at pH 5 and log K-1 = 4.57(3), log K-2 = 4.03(1) a
t pH 6.