I would like to know when the term Pi (inorganic phosphate) was introduced in the representation of biochemical reactions, how it was originally defined, and the justification given then for using it rather than an individual species of phosphate.
(I would also be interested in the current justification, but that’s probably another question.)
Let me provide some background to my question. Phosphoric acid (H3PO4) has three ionizations, which produce successively the species: dihydrogen phosphate (H2PO4–), monohydrogen phosphate (HPO42–) and orthophosphate (PO43–). At pH 7.4, according to the Wikipedia entry on phosphate, the main species are the mono- and di-hydrogen phosphates (61% and 39% respectively). The term Pi must have been introduced in the 1950s at latest (perhaps before the war), at a time when there would have been little knowledge of the nature of the species involved in reactions involving phosphate — certainly not at the active sites of enzymes.
One of the reasons I am curious to know how the term was introduced is the extent to which it persists in 21st century biochemical text books, where it would seem that many authors either do not know or do not care to explain to their readers why they are still using it at a time when much more is known about the reaction mechanisms. Neither of two well-known texts explain the different ionizations of phosphate, and give only parenthetical definitions in terms of a single species — different in each case: Berg et al. referred to Pi as orthophosphate, whereas Nelson and Cox’s, Lehninger Principles of Biochemistry referred to it as HPO42–.
Acknowledgement: This question was provoked by the SE-Biology question — Where is the H+ ion in this step of glycolysis coming from?