Coagulation of Hydrophobic Ionic Associates of Cetyltrimethylammonium Bromide and Carrageenan

In aqueous solutions, cetyltrimethylammonium cations bind to carrageenan polyanions, and the resulting ionic associates form macroscopic aggregates due to hydrophobic interaction. At certain ratios of cetyltrimethylammonium to carrageenan, the resulting colloidal particles auto-flocculate. According to visual observations, the ratio ranges from 1 to 3 mmol/g; otherwise the suspensions are stable. By measuring the sedimentation rate and particle size distribution, the most extensive flocculation was found to be from 1.7 to 2.3 mmol/g. The ratio corresponding to the fastest auto-flocculation was precisely determined by titrating the reagents with small increments and recording the turbidity. The turbidimetric titration plots contain distinct break points corresponding to the most extensive flocculation. These break points occur at the same ratio of carrageenan to cetyltrimethylammonium over a wide range of reagent concentrations. The precise values of the critical ratio were found to be 1.78 and 1.53 mmol/g, respectively, during the titration of cetyltrimethylammonium with carrageenan and vice versa. The number of anionic sulfate groups in carrageenan was measured by ICP OES and found to be 1.35 mmol/g. This value is consistent with the critical ratio of the auto-flocculation.