Methods of test for sulphuric acid, oleum and liquid sulphur trioxide

2015 ◽  
1962 ◽  
Vol 40 (4) ◽  
pp. 658-674 ◽  
Author(s):  
R. J. Gillespie ◽  
E. A. Robinson

The Raman spectra of oleums, i.e. mixtures of sulphur trioxide and sulphuric acid, have been re-examined. Similar measurements on the sulphur trioxide – deuterosulphuric acid (D2SO4) system are also reported. The experimental results and conclusions of previous similar work on oleums are discussed. By comparison of the spectra of oleums with those of the polysulphuryl halides it is shown that the polysulphuric acids H2S2O7 and H2S3O10 are present in this system. The increase in the frequency of the SO2 stretching vibrations with increasing concentration of sulphur trioxide gives evidence for the existence of higher polysulphuric acids such as H2S4O13 at high concentrations of sulphur trioxide. In relatively concentrated oleum, sulphur trioxide monomer and trimer are also present. It is shown that the self-dissociation of liquid H2S2O7 gives mainly molecular H2S2O10 and H2SO4 and not ionic species. The conclusions reached from the interpretation of the Raman spectra of the D2SO4–SO3 system are similar to those arrived at for sulphuric acid oleums. The spectra of solutions of NaHSO4 in oleums were also examined, and are discussed.


1964 ◽  
Vol 42 (5) ◽  
pp. 1113-1122 ◽  
Author(s):  
S. K. Hall ◽  
E. A. Robinson

Cryoscopic and conductimetric studies of a variety of compounds containing S—O bonds have shown that dimethyl sulphoxide behaves as a strong base in sulphuric acid whereas dialkyl sulphones behave as weak bases. In contrast diaryl sulphones and aryl sulphonic acids behave as non-electrolytes.A correlation is established between the basicities of the alkyl sulphones, H2SO4, and the HSO4− ion, and their sulphur–oxygen stretching frequencies. This relation is used to predict the basicities of other compounds containing S—O bonds. In particular it is shown that the basicity of monomeric sulphur trioxide is similar to that of sulphuric acid, and sulphamide is shown to behave as a strong base in sulphuric acid, which implies protonation on a nitrogen atom rather than on oxygen, since the S—O stretching frequencies indicate only weakly basic behavior for O-protonation.


1966 ◽  
Vol 19 (6) ◽  
pp. 931 ◽  
Author(s):  
ECM Grigg ◽  
GR Johnston

The infrared spectra of both gaseous and liquid sulphur trioxide have been investigated between 4000 and 650 cm-1. A gas cell for use with very reactive compounds has been described.


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