The rates of the reduction of Cr(VI) with H2O2 were measured in NaCl solutions as a function of pH (1.5-4.8), temperature (5-40 degrees C), and ionic strength (I = 0.01-2 M) in the presence of an excess of reductant. The rate of Cr(VI) reduction is described by the general expression -d[Cr(VI)]/dt = k2[Cr(VI)](m)[H2O2](n)[H+](z), where m = 1 and n and z are two interdependent variables. The value of n is a function of pH between 2 and 4 (n = (3 x 10(a))/(1 + 10(a)), where a = -0.25 - 0.58pH + 0.26pH2) leveling off at pH < 2 (where n approximately = 1) and pH > 4 (where n approximately = 3). The rates of Cr(VI) reduction are acid-catalyzed, and the kinetic order z varies from about 1.8-0.5 with increasing H2O2 concentration, according to the equation z = 1.85 - 350.1H2O2 (M) which is valid for [H2O2] < 0.004 M. The values of k2 (M(-(n+z)) min(-1)) are given by k2 = k/[H+](z) = k1/[H2O2](n)[H+](z), where k is the overall rate constant (M(-n) min(-1)) and k, is the pseudo-first-order rate constant (min(-1)). The values of k in the pH range 2-4 have been fitted to the equation log k = 2.14pH - 2.81 with sigma = +/- 0.18. The values of k2 are dependent on pH as well. Most of the results with H2O2 < 3 mM are described by log k2 = 2.87pH - 0.55 with sigma = +/- 0.54. Experimental results suggest that the reduction of Cr(VI) to Cr(III) is controlled by the formation of Cr(V) intermediates. Values of k2 and k calculated from the above equations can be used to evaluate the rates of the reaction in acidic solutions under a wide range of experimental conditions, because the rates are independent of ionic strength, temperature, major ions, and micromolar levels of trace metals (Cu2+, Ni2+, Pb2+). The application of this rate law to environmental conditions suggests that this reaction may have a role in acidic solutions (aerosols and fog droplets) in the presence of high micromolar concentrations of H2O2.
Usnic acid is a biosynthesis product characteristic of several epiphytic lichens such as Evernia, Cladonia and Parmelia. Usnic acid has several interesting biological properties. It is an antibiotic and it also seems to exert an antimitotic action. It has even been postulated that usnic acid can play a role as an environmental indicator, since its concentration varies according to the presence of toxic agents. A series of tests have been run on different biological systems such as fungi, yeasts, plant cells and neoplastic human cell cultures in order to make a general evaluation of the properties of usnic acid and to highlight any analogy between its effects on phylogenetically distant organisms. The results obtained confirm some of the already known properties of usnic acid and identify concentration ranges that are active against cells from different organisms. Furthermore, at low concentrations, the acid displays a capacity to stimulate cell metabolism in some of the biological systems tested.
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