Abstract

The effects of increasing perfluoroalkyl chain length on the molecular properties of viscosity, diffusivity, and ionic conductivity of a series of acid model compounds analogous to comb-branch perfluorinated ionomers functionalized with phosphonic, phosphinic, and sulfonic protogenic groups are reported. Anhydrous proton transport by a Grotthuss-like hopping mechanism was observed to occur efficiently in phosphorus-based fluoroalkylated model acids but only when there is a relatively low perfluoroalkyl content. The decrease in degree of dissociation of the protogenic groups follows the order phosphonic > phosphinic > sulfonic, and the degree of dissociation and the magnitude of ion-ion correlations are approximately independent of chain length.

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