The Yet Another Reaction Program (YARP 2.0) was utilized to study the kinetics of the uncatalyzed rTCA cycle and competing side-reactions involving its intermediates. YARP methodology enumerates the reactions by generic graphical rules to find the potential products with the given reactants. These rules take the form of break n bonds and form m bonds (bnfm), where n and m can vary based on the reaction template. YARP uses these graphical rules to generate potential products and then double-ended transition state search to localize and compare transition states of competing reactions. In this study, the b2f2 reaction enumeration rules were applied to enumerate possible reactions, and the rTCA cycle was decomposed into several elementary reaction steps that conform to the b2f2 reaction rule. To localize the TS of the reaction channel connecting off-cycle species back into the main cycle and the reaction channel connecting two off-cycle species to form parallel cycles adjacent to the main rTCA cycle. The enumeration step was circumvented and established the reactant-product pairs by utilizing the geometries of the off-cycle product and the main cycle intermediate or the two off-cycle species. Ten distinct reactant-product conformer pairs are established, using conformational sampling methods using the CREST package. TS are localized with GFN2-xTB as the low level of theory and wB97XD/def2TZVP in an implicit aqueous environment with the PCM solvation model (ε = 78.4) as the high-level theory. Two sets of calculations were performed, one with just the implicit solvation model of water to account for the solvation effects of the aqueous environment of the biochemical reaction, and the other is the water-catalyzed mechanism. The water-catalyzed reaction mechanism refers to the additional transfer of one or several protons to or from water molecules in the TS and the subsequent alteration of the Potential Energy Surface (PES). The water-catalyzed reaction mechanism is generated by using the graphical enumeration described previously. Subsequently, a water molecule is added in the spatial vicinity of reactive centers in the spatial coordinate files of the reactant-product pairs, to account for the effect of water molecules being present in the solution and their interaction with the reactants and products. All DFT calculations were carried out by Gaussian 16. All GFN2-xTB calculations were performed with the xTB program (version 6.4.0).