Although water's chemical properties are no less important than its exceptional physical properties, its acid-base behavior is relatively poorly understood. In fact, the Grotthus trajectories for ion recombination predicted by density functional theory do not comport well with the almost 100-fold slower diffusive trajectories observed in time-resolved spectroscopy. And, in the reverse reaction, the barrier to autoionization is not well: characterized. Here we develop a self-consistent picture of both processes based,on the occurrence and: role of ultrashort hydrogen bonds. The predicted populations of these special pairs in bulk water are consistent with the high frequency electrodynamics of water and its pressure dependence. The rate-limiting role of the special pairs manifests in autoionization as a two-stage barrier, first to form a contact ion pair and then to separate it by one water molecule. From this configuration, similar frequencies are observed for further separation vs recombination. The requirement of ultrashort hydrogen bonds for proton transfer in autoionization is consistent with the rise in K-W with increasing pressure and:points to a role for density fluctuations in autoionization events. In neutralization,the manifestation of the role of special pairs is the prolonged diffusional process observed in time-resolved spectroscopy experiments: The requirement of special pairs as transition states for proton transfer is less obvious for neutralization in isolated Water chains than in the bulk liquid only:because an unbroken sequence of ultrashort H-bonds is more easily,formed in a 1D H-bonded Chain than in a 3D H-bonded-network.