The high concentrations of hydrogen sulfide found in many oil and gas fields is thought to arise from the oxidation of petroleum hydrocarbons by sulfate—a reaction that reduces the value of the resource. This review, undertaken in order to better understand the geochemistry of TSR reaction in oil field sediments, covers the relevant information on thermochemical sulfate reduction (TSR) to 1991. The theoretical and experimental aspects of TSR reactions (including sulfur and carbon isotope studies) are reviewed and their significance to the geochemical system discussed. The present review agrees with previous suggestions that biochemical reduction of sulfate dominates in sedimentary environments below 120°C, and supports the possibility that reactive sulfur species will oxidize certain organic molecules at meaningful rates in geochemically reasonable reaction periods at temperatures above 175°C. We conclude that under typical petroleum reservoir reaction conditions, both elemental sulfur and polysulfides are capable of oxidizing some organic molecules under basic conditions. But that sulfate alone will not react unless lower oxidation state sulfur is present. The possible interaction of low-valence-state sulfur with sulfate to form TSR active oxidants is examined. both H2S and SO
 4
 2−
 are required for the formation of active polysufide reductants (e.g. thiosulfate or polythionates) in TSR systems. Such intermediates can serve to lower the overall activation energy of the oxidation of hydrocarbons by sulfate via thermal generation of sulfur radicals that can function as TSR active oxidants in many oil field sediments. We suggest that some proposed chemical mechanisms for TSR need to be experimentally verified and the results re-interpreted with respect to TSR relations in geologic systems.

Thermochemical sulfate reduction a review

Advances in sulfur chemistry for treatment of acid gases

http://www.pvv.org/~stm/research/thermofluid.pdf

CO2 transport: Data and models – A review

Catalytic conversion of aryl triazenes into aryl sulfonamides using sulfur dioxide as the sulfonyl source.

Hydrothermal dewatering of lower rank coals. 2. Effects of coal characteristics for a range of Australian and international coals

Equilibrium in the reaction between water and sulfur at high temperatures. the dissociation of hydrogen sulfide.

/pdf/a-preliminary-study-of-reversible-reactions-of-sulfur-12fmrjret6.pdf

A preliminary study of reversible reactions of sulfur compounds.

/pdf/equilibrium-in-the-reaction-between-sulfur-dioxide-and-water-7sh0zfd8qj.pdf

F. Russell v. Bichowsky

Papers

Equilibrium in the reaction between water and sulfur at high temperatures. the dissociation of hydrogen sulfide.

A preliminary study of reversible reactions of sulfur compounds.

Equilibrium in the reaction between sulfur dioxide and water.

The heat of formation of molecular hydrogen1

Free energy of the thiosulfate ion