Ammonium salts of sulfur-containing oxyanions resulting from reaction of sulfur dioxide with aqueous solutions of diethylentriamine and bis(hexamethylene)triamine

Abstract

Interaction in the system «sulfur dioxide–diethylenetriamine (or bis- (hexamethylene)triamine)–water–air oxygen» results in a mixture of double salts (diethylenetriammonium bis(sulfito)-dithionate (Ia) and bis(sulfito)-sulfate trihydrate diethylenetriammonium (Ib)) or bis(hexamethylene)triammonium sulfate (II). The obtained ammonium salts of sulfur-containing oxyanions Ia, Ib, and II were characterized by the methods of elemental analysis, X-ray structural analysis, X-ray powder diffraction, IR spectroscopy, and mass spectrometry. Compound Ia crystallizes in monoclinic syngony (space group Ñ2/ñ, a=28.1583(5) Å, b=6.84450(10) Å, c=10.8351(2) Å, β=93.776(2)0, V=2083.71(6) Å3, Z=4). Compound Ib crystallizes in rhombic syngony (space group Pbcn, a=18.9777(13) Å, b=10.3131(8) Å, c=11.5414(10) Å, V=2258.9(3) Å 3, Z=4). Compound II crystallizes in triclinic syngony (space group P-1, a=11.347(3) Å, b=11.700(5) Å, c=18.913(4) Å, α=95.22(3)0, β=92,52(2)0, γ=118,27(4)0, V=2191,36 Å3, Z=2). The IR spectrum of the mixture of salts Ia and Ib shows the valence vibrations of ν(SO) of sulfite anion (ν1 and ν3), represented by bands at 955, 931, 907, 1026, and 1006 cm–1. Two bands at 566 and 493 cm–1 are the result of the splitting of a doubly degenerate out-of-plane deformation vibration of the ν4 (E) of dithionate anion. The bands at 1127 and 1078 cm–1 correspond to the oscillations of νas and νs of sulfate anion (SO42–). A decrease in the symmetry of the SO42– anion as a result of salt formation is accompanied by the appearance of the band ν1 (A1) at 980 cm–1 in its spectrum.