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The enol form of pyruvate is unstable and tautomerizes rapidly and nonenzymatically to the more stable keto form, that predominates at pH 7.

So, the high phosphoryl-transfer potential of PEP is due to the subsequent enol-keto tautomerization of pyruvate. What happens is that the phosphoryl group traps PEP in its unstable enol form. Substrate-level phosphorylation is defined as the production of ATP by the transfer of a phosphoryl group from a substrate to ADP, a process involving chemical intermediates and soluble enzymes.
When, in the last step of glycolysis, phosphoenolpyruvate donates the phosphoryl group to ADP, ATP and the enol form of pyruvate are formed. 61.9 kJ/mol (-14.8 kcal/mol) for phosphoenolpyruvate, an enol phosphate. The reaction is essentially irreversible, with a ΔG°’ of -31.4 kJ/mol (-7.5 kcal/mol), and a ΔG of -16.7 kJ/mol (-4.0 kcal/mol), largely due, as anticipated in the previous paragraph, to the tautomerization of the pyruvate from the enol form to the more stable keto form.
The remaining energy, -31.4 kJ/mol (-7.5 kcal/mol), is the driving force that makes the reaction proceed towards ATP production.

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