Sulfur thermochemistry

Other major sources of data on the thermochemistry of sulfur-containing compounds are the review by Benson19, which is of particular value in evaluating data on radicals and other labile species, and the review of the present author on the thermochemistry of the inorganic S—O—F compounds20. 

G. Waddington, S. Sunner, W. N. Hubbard. Combustion in a Bomb of Organic Sulfur Compounds. In Experimental Thermochemistry, vol. 1 F. D. Rossini, Ed. Interscience New York, 1956 chapter 7. 

The thermochemistry of sulfur radicals in the gas phase has been reviewed. Methylsulfonyl radicals and cations have been produced by femtosecond collisional electron transfer in the gas phase. When formed by vertical collisional electron transfer from cation CH3SO2+, radical CH3S02 dissociates to CH3 and SO2. Radical CH30S0 exists as a mixture of syn (19a) and anti (19b) isomers which are stable when formed by collisional electron transfer to the corresponding cation. Dissociation of both isomers of CH30S0 formed CH3 and SO2 via isomerization to methylsulfonyl radical. An ab initio study on the formation of the thiyl peroxyl radical has also been reported. Julolidylthiyl radicals (20) were formed by femtosecond photo-dissociation of the corresponding disulfide and have been observed... 

NQR, 22 216 olefin complexes of, 4 85 in organogermanium compounds, 27 141,143 oxyfluoride, properties of, 11 29 pentacarbonyl dimets of sulfur oxydifluoride imide, 19 203-205 pentafluoride, structure, 27 102 peroxides, 6 325-326 phthalocyanine, 7 54 physical properties of, 11 18 polysulfide complexes, 31 100, 102 envelope conformation, 31 115 synthesis, 31 103-104 [Pt[15]aneS5) f, 35 75, 77 reaction with fluorinated peroxides, 16 120 salts, lattice energy and thermochemistry, 22 52-56... 

The present volume comprises 17 chapters, written by 27 authors from 11 countries, and deals with theoretical aspects and structural chemistry of peroxy compounds, with their thermochemistry, O NMR spectra and analysis, extensively with synthesis of cyclic peroxides and with the uses of peroxides in synthesis, and with peroxides in biological systems. Heterocyclic peroxides, containing silicon, germanium, sulfur and phosphorus, as well as transition metal peroxides are treated in several chapters. Special chapters deal with allylic peroxides, advances in the chemistry of dioxiranes and dioxetanes, and chemiluminescence of peroxide and with polar effects of their decomposition. A chapter on anti-malarial and anti-tumor peroxides, a hot topic in recent research of peroxides, closes the book. 

Pilcher73 has recently reviewed the experimental data for a variety of carbonyl and thio-carbonyl compounds. Enthalpies of formation for dithiocarbonic acids, R2N—C(=S)SH, thioamides and thioureas were determined by standard calorimetric methods. For an important, older review on the thermochemistry and thermochemical kinetics of sulfur-containing compounds, see work of Benson74. 

Armstrong DA (1999) Thermochemistry of sulfur radicals. In Alfassi ZB (ed) S-centered radicals. Wiley, New York, pp 27-61... 

Griller D, Simoes JAM, Wayner DDM (1990) Thermochemistry of sulfur-centered intermediates. In Chatgilialoglu C, Asmus K-D (eds) Sulfur-centered reactive intermediates in chemistry and biology. Plenum, New York, pp 37-52... 

Phosphorus—selenium bonds, alkyne additions, 10, 782 Phosphorus—sulfur bonds, alkyne additions, 10, 781 Phosphorus ylides with gold(I), 2, 275 with trinuclear Os clusters, 6, 740 Phosphoylides, actinide complexes, 4, 203 Photoacoustic calorimetry, in thermochemistry, 1, 612-613 Photoactive molecular devices, and -[RefCO) ,] fragment, 5, 886... 

Experimental Thermochemistry of Heterocycles and Their Aromaticity A Study of Nitrogen, Oxygen, and Sulfur Derivatives of Indane and Indene... 

Keywords aromaticity, indane, indene, nitrogen-containing heterocycles, oxygen-containing heterocycles, sulfur-containing heterocycles, thermochemistry... 

It is to be recalled that not only is there ambiguity as to the products of combustion of any antimony-containing species (cf. Reference 28), thermochemical studies of sulfur compounds show related complications. (See for example, the discussion in W. N. Hubbard, D. W. Scott and G. Waddington, in Experimental Thermochemistry Measurements of Heats of Reaction (Ed. F. D. Rossini), Interscience, New York, 1956.)... 

In a recent review of the thermochemistry of sulfur-containing species, Benson (4) has shown that in R S compounds with R... 

Benson, S. W. (1978). Thermochemistry and kinetics of sulfur-containing molecules and radicals. Chem. Rev. 78, 23-35. 

Any large scale process for reducing sulfur dioxide to elemental sulfur will likely depend on a fossil fuel. Whether the fuel is used to reduce sulfur to such compounds as hydrogen sulfide or carbonyl sulfide which are then used as the reductant for sulfur dioxide or whether the fuel itself is the sulfur dioxide reductant, the overall thermochemistry is similar. 

Finally, a comprehensive study of the thermochemistry of sulfur fluoride cations and neutrals was performed (Fisher et al., 1992). Endothermic charge-transfer reactions of several of the SF+ ions were examined. Analyses of these cross sections yielded the ionization energies of SF from reactions with Xe of SF3 from reactions with CH3I, NO, and C HsBr of SF4 from reactions with Xe and O2 and of SF5 from reactions with NO, C6H5CF3, and CH3I. IE(SF2) was not measured in our work, as a precise photoelectron value (10.08 0.05 eV) was already available in the literature (DeLeeuw et al., 1978). Some of our values... 

---