Table 4.

Thermochemistries (in kcal/mol) of the various decomposition pathways at the PCM/B3LYP/6-31G**//B3LYP/6-31G* level of theory.

hydrolysis
DMPO•-X + H2O	DMPO•-OH + HX	ΔG298K,aq	ΔH298K,aq
DMPO•-SO3−	HSO3−	−3.5	7.2
DMPO•-OSO2−	HSO3−	−1.8	9.8
DMPO•-OSO3−	HSO4−	−2.6	3.9
intramolecular cleavage
1
DMPO•-OXn	DMPO•-O− + XOn-1	ΔG298K,aq	ΔH298K,aq
DMPO•-OSO2−	SO2	16.9	29.8
DMPO•-OSO3−	SO3	48.8	62.4
2
		ΔG298K,aq	ΔH298K,aq
DMPO•-O−, H2O	DMPO•-OH, OH−	5.4	59.0
net intramolecular cleavage energetics
Adduct		ΔG298K,aq	ΔH298K,aq
DMPO•-OSO2−		22.4	88.8
DMPO•-OSO3−		57.2	121.4