AbstractThe structure of the cellulose solvent ferric sodium tartrate (FeTNa) was studied using a sensitive adiabatic calorimeter. FeTNa was found to be a typical transition metal complex in which three tartrate ligands add in a stepwise fashion to iron. The structure of FeTNa first proposed by Franke is thus confirmed. The equilibrium constant for the addition of the third tartrate ligand to iron is approximately 100, a value typical of those for other cellulose‐dissolving metal complexes. There is no calorimetric evidence for addition of more than three tartrate molecules to iron. The increase in molar heats of reaction with increasing ionic strength is consistent with dilute electrolyte solution theory. Based on these data, the probable reaction between FeTNa and cellulose has been postulate