| Summary: | A series of hydroxylamine-N,N-disulphonate and nitrosodisulphonate
salts with monovalent cations have beeh prepared
and characterized.
The salts of the hydroxylamine-N,N-disulphonate ion
crystallize with either [(S03)2NOH]2-
ions or {[ (S03)2N0]2H}5-
groups. In general, salts with [(S03)2NOH]2- ions crystallized
from basic aqueous solutions when the pH was less than 11.5
while those containing {[ (S03)2N0]2H}5-
groups form on crystallization
from more strongly basic aqueous solutions.
Nitrosodisulphonate ions, in low concentration, can enter
the crystal lattices of salts containing [(S03)2NOH]2- ions,
presumably substitutionally for the [(S03)2NOH]2- ion. This was
confirmed by e.p.r. measurements.
Species with S=l form on Co60 irradiation of the salts
containing· (S03)2N0]2H}5-
groups. These species have
zero-field splittings which suggest they arise from the net loss
of a hydride ion from the (S03)2N0]2H}5- group.
Two crystalline modifications of potassium nitrosodisulphonate
and two crystalline modifications of rubidium
nitrosodisulphonate were found to have thermally accessible
triplet states. This was concluded from measurements of the
zero-field splitting, the temperature dependence of the static
magnetic susceptibility and the temperature dependence of the
e.p.r. absorption area for powdered samples or each of these
salts. Measurements of the temperature dependences of the
line width and line separation of the e.p.r. signals arising
from the S=l species in each of the crystalline modifications
of potassium nitrosodisulphonate suggest that these S=l excitations
are excitons.
Measurements of the temperature dependences of the static
magnetic susceptibility (100-300 K) of powdered samples of the
other nitrosodisulphonate salts prepared show that these salts
contain S=½ nitrosodisulphonate ions. The room temperature
e.p.r. powder spectra of these salts are also reported.
A catalog of the infrared spectra (in KBr) or the
hydroxylamine-N,N-disulphonate and nitrosodisulphonate salts
prepared is given, in addition to a catalog of the powder
reflectance spectra of the nitrosodisulphonate salts.
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