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Abstract The signal amplification by reversible exchange process (SABRE) enhances NMR signals by unlocking hidden polarization in parahydrogen through interactions with to-be-hyperpolarized substrate molecules when both are transiently bound to an Ir-based organometallic catalyst. Recent efforts focus on optimizing polarization transfer from parahydrogen-derived hydride ligands to the substrate in SABRE. However, this requires quantitative information on ligand exchange rates, which common NMR techniques struggle to provide. Here, we introduce an experimental spin order transfer sequence, with readout occurring at¹⁵N nuclei directly interacting with the catalyst. Enhanced¹⁵N NMR signals overcome sensitivity challenges, encoding substrate dissociation rates. This methodology enables robust data fitting to ligand exchange models, yielding substrate dissociation rate constants with higher precision than classical 1D and 2D¹H NMR approaches. This refinement improves the accuracy of key activation enthalpy ΔH^‡and entropy ΔS^‡estimates. Furthermore, the higher chemical shift dispersion provided by enhanced¹⁵N NMR reveals the kinetics of substrate dissociation for acetonitrile and metronidazole, previously inaccessible via¹H NMR due to small chemical shift differences between free and Ir-bound substrates. The presented approach can be successfully applied not only to isotopically enriched substrates but also to compounds with natural abundance of the to-be-hyperpolarized heteronuclei.