Titrimetric Methods of Analysis
Titrimetry, in which we measure the volume of a reagent
reacting stoichiometrically with the analyte, first
appeared as an analytical method in the
early eighteenth century. Unlike gravimetry, titrimetry initially did
not receive wide
acceptance as an analytical technique. Many prominent late-nineteenth century
analytical chemists preferred gravimetry over titrimetry and few of the standard
texts from that era
include titrimetric methods. By the early
twentieth century, however, titrimetry began
to replace gravimetry as the most
commonly used analytical method.
Interestingly, precipitation
gravimetry developed in the absence of a theory of precipitation. The
relationship between the
precipitate’s mass and the mass of analyte, called a gravimetric factor,
was determined experimentally by taking known
masses of analyte
(an external standardization). Gravimetric factors could not be calculated
using the precipitation reaction’s stoichiometry because chemical formulas and atomic weights
were not yet available! Unlike
gravimetry, the growth and acceptance of titrimetry required a deeper
understanding of stoichiometry, thermodynamics, and chemical equilibria. By the early
twentieth century the
accuracy and precision of titrimetric methods were comparable to that of gravimetry,
establishing titrimetry as an accepted analytical technique.
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