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Additional info for Reaction Mechanisms in Sulphuric Acid: And other Strong Acid Solutions
1963) that one could assume this effect to be linearly dependent on acidity and thus obtain corrected e values by an extrapolation procedure. Taking all this into account, it may be concluded that the cumulative error in the evaluation of acidity functions arises mainly from errors in the deter mination of the pK of individual indicators used in the overlap procedure (Vinnik, 1966). The pK of the first indicator may be known to ±(0-02-0-04) units. If the logarithms of the ionization ratios of all subsequent indicators are determinable to ±(0-02-0-04) units, which is the usual accuracy obtainable, the error in the acidity function will be the sum of such errors for all indicators involved in its determination.
Also, similar problems arise in measurements with all kinds of indicators. These questions will be discussed in the present section. 1. 1. Principles and Methods The measurement of the ionization ratios of indicators is carried out as a rule spectrophotometrically, because the unionized and the ionized forms of the indicators differ considerably in their absorption spectra, both in the positions of maximum absorption and in the values of specific absorption coefficients. It is sufficient if only one form has a pronounced absorption maximum, but more accurate determination of ionization ratios is possible if both forms give well-defined peaks sufficiently far apart.
However, a calculation of changes in the spacings from volume changes would be difficult. The important point is that the diffraction pattern persists throughout the whole sulphuric acid/water concentration range, indicating a high degree of internal order in all the mixtures. 5. r. spectrum. The chemical shifts of that line relative to pure water as external reference have been measured by several authors (Gutowsky and Saika, 1953; Hood and Reilly, 1957; Gillespie and White, 1960). A down-field shift is observed with increasing acid concentration, which goes through a maximum at about 17 mol litre -1 and then decreases at still higher concentrations.