The kinetic isotope effect in the chemical reduction of sulphate

Harrison, A. G.; Thode, H. G.

doi:10.1039/tf9575301648

Cited by 151 publications

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“…The stage that determines the isotope effect is the reduction of sulfate to sulfite. That is, the isotope effect occurs when the sulfur-ox ygen bonds in the sulfate break (Harrison and Thode, 1957). Thus, the isotope effect during sulfate reduction by acetic acid may be depen dent on the atomic hydrogen produced during the decomposition of the reducing agents.…”

Section: Temp (°C)mentioning

confidence: 99%

“…Table 4 gives the comparison of the kinetic effects estimated with other data. The isotope fractionation factors at 0 and 25'C were ob tained from theoretical considerations (Harrison and Thode, 1957). Those at 50 and 100°C were derived from the reduction of sulfate to hydrogen sulfide (Harrison and Thode, 1957;Grinenko et al, 1969).…”

Section: Temp (°C)mentioning

confidence: 99%

“…The isotope fractionation factors at 0 and 25'C were ob tained from theoretical considerations (Harrison and Thode, 1957). Those at 50 and 100°C were derived from the reduction of sulfate to hydrogen sulfide (Harrison and Thode, 1957;Grinenko et al, 1969). The sulfates at tempera ture from 138 to 210°C were reduced to sulfurous acid with evolved atomic hydrogen by the addition of acid to a metallic tin (Grinenko et T: theoretical; A.H.: atomic hydrogen; 0-50°C (Harrison and Thode, 1957); 100--210°C (Grinenko et al, 1969); *: These values were calculated from Eq .…”

Section: Temp (°C)mentioning

confidence: 99%

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The role of organic acid in the abiogenic reduction of sulfate and the sulfur isotope effect.

1990

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Abiogenic reduction of sulfate by acetic acid has been conducted at temperatures ranging from 241 to 340°C. The sulfides produced and the remaining sulfates have been chemically and isotopically quan tified. The reaction of the aqueous sulfate reduction obey first-order kinetics. The rate constants are strongly dependent on temperature. The temperature dependence of the reaction rate (min-') is given by the following rate law: log k=-10.3 x 103/T+15.1. The activation energy for the reaction of sulfate reduction is 208 kJ mol-1.

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Section: Temp (°C)mentioning

confidence: 99%

Section: Temp (°C)mentioning

confidence: 99%

Section: Temp (°C)mentioning

confidence: 99%

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The role of organic acid in the abiogenic reduction of sulfate and the sulfur isotope effect.

1990

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“…Consequently, the accurate estimation of a sulphur source generally requires many additional data (such as pH, jD2, and 2') because oxidation-reduction processes induce large isotopic fractionations between sulphides and coeval dissolved sulphates (Ohmoto, 1972;Arnold and Sheppard, 1981). Similar difficulties occur if bacterial sulphate reducers are involved in near surface marine environments because the isotopic composition of biogenic SH, depends upon nutrient supply, reduction rate, sulphate concentration, and temperature (Harrison and Thode, 1957). Fortunately, such a difficulty is not encountered in the present study because only very small fractionation effects are involved both in the oxidation of sulphides into sulphates at low temperatures and in gypsum crystallization (Thode and Monsters, 1965;Krouse, 1980;Pearson and Rightmire, 1980).…”

Section: The Isotopic Composition Of Sulphurmentioning

confidence: 99%

The origin of gypsum in Vertisols in New Caledonia determined by isotopic characteristics of sulphur

Podwojewski¹,

Arnold

1994

Geoderma

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Gypsum crystals occur in Vertisols on the west coast of New Caledonia. These soils are derived from the weathering of basic rocks that contain no gypsum. The sulphur isotopic ratio 34S/32S was used as tracer to identify the origin of the gypsum. A total of 26 measurements of 1 3~~s were made on gypsum crystals from the Vertisols and compared to those of continental sulphates and to marine gypsum in tidal flats. The S34S value of the crystals located in New Caledonian Vertisols decreases with increasing distance from the coast. This suggests that the gypsum in the Vertisols comes from two sources: an oceanic source where the major part of the sulphur is introduced by atmospheric precipitation, and a continental source where sulphides disseminated in various subsurface deposits are oxidized. Gypsum from atmospheric precipitation penetrates the Vertisols through vertical cracks that probably formed in dry seasons during the last glacial period.

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“…The fractionation decreases with the increase of temperature. At the temperature of 100˚C, fractionation is about 20‰; when the temperature reaches 150˚C, fractionation is about 15‰; at 200˚C, fractionation is only 10‰ (Harrison and Thode, 1957;Husain and Krouse, 1978;Kiyosu and Krouse, 1990).…”

Section: Energy Exploration and Exploitationmentioning

confidence: 99%

Geochemistry Characteristics of Hydrogen Sulphide-Bearing Gas Pools in Sichuan Basin

Li¹,

Jin²,

Cui³

et al. 2014

Energy Exploration & Exploitation

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Sichuan Basin is the oil and gas bearing basin that is discovered in China, with the most hydrogen sulfide gas pool and the greatest reserve. In this article, gas pools with high hydrogen sulfide in Sichuan Basin were taken as the object of study; the geochemistry characteristic of natural gas was systematically studied, and the origin of natural gas with hydrogen sulfide in Sichuan Basin was discussed. The hydrogen sulfide content in the hydrogen sulfide gas pools of Sichuan Basin is 0.6%-14.5%; the sulfur isotope values of hydrogen sulfide gas have a close relationship with the sulfur isotope values of anhydrite in the same reservoir, and the sulfur isotope fractionation between the anhydrite and the H 2 S is 4‰-14‰, showing that the H 2 S in natural gas and the anhydrite in reservoir have the same sulfur source, the H 2 S in natural gas is the product of TSR reaction. The relationship among the hydrogen sulfide content in the gas pool, the hydrogen isotope of methane and the sulphur isotope of hydrogen sulfide is not obvious; but the high hydrogen sulfide content corresponds to the heavier ethane carbon isotope composition, and the carbon isotope of carbon dioxide is lower than -10‰, which belongs to the organic origin and has further verified the fact of TSR occurrence in the reservoir. There is the phenomenon of carbon isotopic reversal of methane and ethane in some areas of the Huanglongchang gas field, Wubaiti gas field and Puguang gas field in the Northeast Sichuan as well as Weiyuan gas field in South Sichuan, which is mainly caused by the later period of cracking-based gas-production process of the crude oil. TSR has less influence on these gas pools.Keywords: Geochemical characteristics, Sulfur isotope, H 2 S-bearing gas reservoirs, Sichuan Basin INTRODUCTIONHydrogen sulfide is widely found in natural gas reservoirs both in China and abroad (Sokolov et al., 1971;Anderson et al., 1987;Machel et al., 1995;Desrocher et al., 2004;Zhu et al., 2005), where the contents of hydrogen sulfide are usually less than 5%. The content of hydrogen sulfide at Jurassic limestone reservoir in South Texas of the US is as high as 98%, ranking the first in the world; that at Zhao Lanzhuang gas field in Jizhong depression is as high as 92% (Dai, 1985). China's hydrogen sulfidebearing natural gases are mainly distributed in Sichuan Basin, Bohai Gulf Basin, Erdos Basin and Tarim Basin with the contents of hydrogen sulfide usually less than 0.5%. The existence of hydrogen sulfide in natural gas brings great danger to the exploration and safety production of natural gas. Currently, most of the hydrogen sulfide-bearing gas fields with industrial value found in the world are distributed in carbonate rock strata. The extensively distributed marine carbonate area in China is an important field for China's oil and gas exploration in the future. Therefore, the research on the genesis, enrichment and distribution characteristics of hydrogen sulfide has great significance on China's marine oil and gas exploration.Foreign schola...

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The kinetic isotope effect in the chemical reduction of sulphate

Abstract: The kinetic isotope effect in the chemical reduction of sulphate to sulphide was investigated over the temperature range from 18 to 50°C. S32O:-was found to react 2.2 % faster than S340:-, in agreement with theoretical calculations based on statistical mechanical methods.

Cited by 151 publications

References 0 publications

The role of organic acid in the abiogenic reduction of sulfate and the sulfur isotope effect.

The role of organic acid in the abiogenic reduction of sulfate and the sulfur isotope effect.

The origin of gypsum in Vertisols in New Caledonia determined by isotopic characteristics of sulphur

Geochemistry Characteristics of Hydrogen Sulphide-Bearing Gas Pools in Sichuan Basin

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