Heterogeneous deacetylation of alpha- and beta-chitins from shrimp shells and squid pens were comparatively studied. Each deacetylated sample, recovered after neutralization, was fractionated according to a water-soluble and insoluble fraction (pH 8.5). The systematic study of DAs, crystallinity changes, and distribution of N-acetylglucosamine residues were performed on the two kinds of fractions. For the two fractions resulting from a deacetylation in the presence of 50% (w/v) NaOH, for temperatures ranging from 80 to 110 degreesC, the activation energies of the reactions were found close to 39.9 +/- 1.0 and 42.8 +/-1.8 kJ mol(-1) and the frequency factors of collision were of 7.2 +/-2.4 and 54.4 +/- 18.5 10(3) min(-1), for alpha- and beta-chitins, respectively. Deacetylations of water-soluble and insoluble fractions were compared, and the major role played by the crystallinity level during deacetylation was evidenced and, thereafter, the role of the nature of the starting chitins on the chemical behavior. Thus, in some conditions, we observed critical values of DDA where the structures were becoming fully amorphous.