Rates of Paramagnetic Pulse Reactions by Nuclear Magnetic Resonance

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Abstract
Certain fast chemical reactions involving both paramagnetic and diamagnetic molecular species are termed ``paramagnetic pulse'' reactions when each reaction event results in a change in a large hyperfine magnetic field acting at one or more of the molecular nuclei. The frequency distribution of the magnetic pulses is directly related to the reaction rate. The hyperfine intensity and frequency distribution of the paramagnetic pulses affects the nuclear resonance (NMR) line shapes. The Bloch equations are used to establish a quantitative relation between nuclear resonance line shape, nuclear, and electron relaxation times, and the reaction rate. The theory is discussed in terms of the Cu63 NMR work of McConnell and Weaver on electron exchange between Cu++ and Cu+ ions in hydrochloric acid solutions, and the H1 NMR work of Bruce, Norberg, and Weissman on the electron exchange between neutral and positive ion molecules of N,N′‐tetramethyl‐p‐phenylenediamine.