Acceleration mechanism of chemical reaction by freezing: The reaction of nitrous acid with dissolved oxygen

The oxidation of nitrite by dissolved oxygen to form nitrate is known to be accelerated ca. 10(5) times by the freezing of the aqueous solution.(1) Here we report a detailed study on the acceleration mechanism of the above-mentioned oxidation. The reaction was studied at pH values between 3.0 and 5.6 at various freezing rates, by different freezing methods, and with and without additional sails. The effect of freezing which induced concentration (freeze concentration) of reactants into the unfrozen bulk solution was too small to explain the acceleration factor of ca. 10(5). Nitrate formations were completely prevented by addition of salts, such as NaCl and KCl, which make the freezing potential of ice negative, while the reaction was not affected by addition of salts, such as Na2SO4 and NH4Cl, which make the freezing potential of ice positive. When a sample solution was frozen in such a way as to form a single crystal of ice, most nitrite was exclusively liberated from the ice to the gas phase. This observation suggests the importance of ice in the polycrystalline form to retain nitrite during freezing. When freezing begins, grains of crystalline ice begin to grow. The solutes are rejected from the ice and concentrated in the interfacial water layer by assistance of the electrostatic force generated by the freezing potential. At a certain stage of freezing, the water layer is completely confined by the walls of some ice grains. Protons move from the ice phase to the unfrozen solution surrounded by the ice walls to neutralize the electric potential generated, and thus the pH of the unfrozen solution decreases. As a result, the reactant species, HNO2, increased more in the unfrozen solution. After this stage, the concentrations of the reactants in the unfrozen solution abruptly increase resulting in the acceleration of the rate of formation of nitrate. On the basis of the above mechanism, the concentration factor fur nitrite was calculated as 2.4 x 10(3). The validity of this mechanism is further discussed.