The rate constants of carbonate radical anion (CO3-) reaction with organic molecules, mainly of environmental interest, were collected from the literature and structure effects were discussed together with methods of rate constant determination and reaction mechanisms. These rate constants are essential for modelling chemical processes taking place with participation of reactive radicals in the environment determining the persistence of certain toxic compounds. The rate constants span over a very wide range from 102 to 109 mol-1 dm3 s-1, but, even the highest values are smaller by a factor of 2-5 as the diffusion controlled limit. This survey shows that only those molecules have high rate constants in the 107-109 mol-1 dm3 s-1 range which have special electron rich part(s). These molecules are removed selectively in CO3- reactions. Such electron rich moiety is the NH2 group attached to an aromatic ring. High vales were measured e.g., for most of anilines or the sulfonamide antibiotics. -CO group attached to the N-atom (in acetanilides and in phenylurea herbicides), or strong electron withdrawing substituents on benzene ring strongly decrease the rate constant. High values were also measured for aromatic molecules with dissociated -OH group (O-, phenoxides). The thioether group (e.g., in amino acids, or in fenthion or phorate insecticides) also activates the molecules in CO3- reactions.
Superabsorbent hydrogels show a large potential in a wide array of applications due to their unique properties. Carboxymethylcellulose (CMC) is a commercially available water-soluble cellulose derivative of major interest in the hydrogel synthesis. High-energy irradiation allows the chemical crosslinking without the use of crosslinking agents, while the introduction of other natural or synthetic polymers offers a convenient way to modify the gels. In this study we examined the effect of the addition of starch, a low-cost renewable polysaccharide, on the properties of carboxymethylcellulose-based hydrogels. Superabsorbent gels were prepared by gamma irradiation from aqueous mixtures of carboxymethylcellulose and starch. The partial replacement of CMC with starch improved the gel fraction, while a slight increase in the water uptake was also observed. However, very high starch content had a negative impact on the gelation, resulting in a decrease in gel fraction. Moreover, higher solute concentrations were preferred for the gelation of CMC/starch than for pure CMC. Hydrogels containing 30% starch showed the best properties: a water uptake of ~350 gwater/ggel was achieved with ~55% gel fraction synthesized from 15 w/w% solutions at 20 kGy. Heterogeneous gel structure was observed: the starch granules and fragments were dispersed in the CMC matrix. The swelling of CMC/starch gels showed a high sensitivity to the ionic strength in water due to the CMC component. However, the mixed gels are less sensitive to the ionic strength than pure CMC gels. The introduction of starch to carboxymethylcellulose systems led to improved properties. Such gels showed higher water uptake, especially in an environment with high electrolyte concentration. CMC/starch hydrogels may offer a cheaper, superior alternative compared to pure cellulose derivative-based gels depending on the application.