Theory of energy flux and polarization changes of a radio wave with two magnetoionic components undergoing self demodulation in the ionosphere

Abstract
The interionic reaction between Co(NH$_3$)$_5$Br$^{2+}$ and OH$^-$, i.e. the alkaline hydrolysis reaction, was studied in the presence of sodium polyethylene-sulphonate or polybrene (1, 5-dimethyl-1,5-diazaundecamethylenepoly-methobromide) under high pressure. The reactions were retarded by the addition of the polyelectrolytes, as is generally the case for reactions between oppositely charged ionic species. The volume and entropy of activation were positive in the absence of the polyethylenesulphonate and decreased in its presence. These experimental results indicate that the macro-anions dehydrate the solvated divalent reactant, Co(NH$_3$)$_5$Br$^{2+}$, strongly. From comparison of the observed deceleration effect of sodium polyethylenesulphonate with the Bronsted-Bjerrum-Manning theory, it is suggested for the polyethylenesulphonate-catalysed alkaline hydrolyses that the dehydration effect of the macro-ions is more important than the electrostatic stabilization effect. On the other hand, the deceleration by polybrene is in good agreement with the theory, suggesting that the influence of the polybrene is mainly due to the electrostatic stabilization of the reactants, but not to the dehydration by the polymer. A linear relation is noted between the volume and the entropy of activation for aquations and alkaline hydrolysis of Co(NH$_3$)$_5$Br$^{2+}$ in the presence of polystyrenesulphonate and polyethylenesulphonate.

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