Amongst the simplest reactions in chemical kinetics are those involving an interchange between a free atom and an atom in a polyatomic molecule. One example of this kind of reaction is the exchange of a deuterium atom with a hydride, namely D + HX = DX + H. The deuterium atoms required to start the reaction may be produced electrically, photochemically, or thermally. The following reactions have been investigated by the thermal method: H + H2, D + D2, D + H2, H + D2, D + NH3. Exchange reactions involving CH4 and NH3 and deuterium atoms produced photochemically have been demonstrated by Taylor, Jungers, Morikava and Benedict, but the results do not lead to quantitative conclusions regarding the mechanism. Geib and Steacie have used H atoms from a Wood’s tube to effect exchange with CH4, NH3, and C2H2, but in the light of subsequent results this method is attended by the intrusion of complicating factors, to be discussed later, whose magnitude is difficult to assess accurately. The subject of the present paper is the investigation over a wide range of operating conditions, of the mercury photosensitized exchange re actions of hydrogen and deuterium with the simplest hydrides, namely water, ammonia, and methane.
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Farkas et al. (1936) studied this question.