Self-ionization sulfuric acid

These results emphasize the fact that ions produced by self-ionization of the solvent, e.g., HsO and 0H in water, ROHt and R0 in alcohols, and NHi" and NHJ in liquid ammonia, do not of necessity possess abnormal conductance, although they frequently do so. It is seen from Table XIX that the conductance of the hydrogen ion in liquid ammonia, i.e., NHi", is normal the same is true for the NHi" ion. The anilinium and pyridinium ions also have normal conductances in the corresponding solvents. The conductance of the HSOr ion in sulfuric acid as solvent is, however, abnormally high it is probable that a Grotthuss type of... 

A few measurements of the conductivities of solutions in sulfuric acid were made by the early workers 6,63,61,63) but there were considerable differences between their results and conclusions, again partly because of a lack of understanding of the solvent self-dissociation and the contribution that it made to the conductivities of the solutions studied. A comprehensive investigation of the conductivities of solutions in sulfuric acid was first made by Gillespie and Wasif 45) and this showed that such measurements were of considerable value in the study of the ionizations of solutes in sulfuric acid. 

Pure sulfuric acid undergoes self-ionization processes. The most important is ... 

Other cases of such self-ionization of a compound where one molecule solvates a proton originating from another are known for example, in pure sulfuric acid 2H2so4 = H3SOJ + HSOj... 

Many other solvents may behave in a similar way. For example, autopro-tolyses of sulfuric acid and ammonia are shown in equation 5 and equation 6, respectively. Such self-ionizations can be written in a general way as in equation 7. 

In the absence of free water, pure sulfuric and phosphoric acids undergo self-ionization. Addition of water, as a proton receptor, promotes the dissociation of the acids. Polymers bearing basic sites, such as ether, alcohol, imine, amide, or... 

The cryoscopic study of sulfoxy compounds was initiated by Szmant et al. (334,335) who found them to be unstable but arrived at the somewhat surprising conclusion that nitro groups increased the basicity of diphenyl sulfone in sulfuric acid. This area was reinvestigated by Gillespie and Passerini (136) who suggested that Szmant did not allow for the self-ionization of sulfuric acid and therefore his f-values were in error by as much as 100%. Accordingly his conclusions were considered to be questionable. 

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