Titrimetry, in which volume serves as the analytical signal, made its first appearance as an analytical method in the early eighteenth century. Titrimetric methods were not well received by the analytical chemists of that era because they could not duplicate the accuracy and precision of a gravimetric analysis. Not surprisingly, few standard texts from the 1700s and 1800s include titrimetric methods of analysis.
Precipitation gravimetry developed as an analytical method without a general theory of precipitation. An empirical relationship between a precipitate’s mass and the mass of analyte—what analytical chemists call a gravimetric factor—was determined experimentally by taking a known mass of analyte through the procedure. Today, we recognize this as an early example of an external standardization. Gravimetric factors were not calculated using the stoichiometry of a precipitation reaction because chemical formulas and atomic weights were not yet available! Unlike gravimetry, the development and acceptance of titrimetry required a deeper understanding of stoichiometry, of thermodynamics, and of chemical equilibria. By the 1900s, the accuracy and precision of titrimetric methods were comparable to that of gravimetric methods, establishing titrimetry as an accepted analytical technique.
Thumbnail: A Winkler titration to determine the concentration of dissolved oxygen in a water sample. The dissolved oxygen has been converted to an equivalent amount of iodine, which is being titrated with thiosulfate using a starch indicator. The blue color in the flask will disappear when all the iodine has been converted to iodide. Image used with permission (CC BY-SA 3.0; Will Woodgate (Cornwall College, UK)).