238. The kinetics of the reaction between carbonyl sulphide and water

Thompson, H. W.; Kearton, C. F.; Lamb, S. A.

doi:10.1039/jr9350001033

Cited by 33 publications

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“…Early research on the reaction of COS with water (hydrolysis) at neutral pHs by Thompson et al (1935) Elliot et al (1987Elliot et al ( , 1989) made more precise measurements of rate constants for both reactions 2.4 and 2.5 between pHs 4-10 and verified the results from the earlier works.…”

supporting

confidence: 60%

The oceanic cycle and global atmospheric budget of carbonyl sulfide

Weiss

1994

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supporting

confidence: 60%

The oceanic cycle and global atmospheric budget of carbonyl sulfide

Weiss

1994

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“…When using COS as a structural analog of C02, one must be careful to avoid artifacts due to the hydrolysis of COS to CO2 and H2S (10,25,29). We have found pH 8.0 to be convenient for the study of HC03-and CO2 transport by Synechococcus UTEX 625 (7,8,(15)(16)(17)(18)(19)(20) (8,19).…”

Section: Resultsmentioning

confidence: 99%

“…1) or at lower pH in the presence of CA (Fig. 2) (25,29). COS is an alternate substrate for Rubisco and the products of the reaction of COS with ribulose-1 ,5-bisphosphate are 3-phosphoglycerate and 3-phospho-l-thioglycerate (13).…”

Section: Discussionmentioning

confidence: 99%

“…COS is stable when dissolved in acidified water but is hydrolyzed in alkaline solution to CO2 and H2S (10,25,29). Hydrolysis proceeds via the monothiocarbonate ion which is unstable at low ionic strength at room temperature (25,29). The rate of COS hydrolysis is slow enough at pH 8.0 or below to allow experiments to be easily performed.…”

Section: Relevant Physical and Chemical Properties Of Cosmentioning

confidence: 99%

“…At a partial pressure of 1 atm at 13.5°C, COS has a solubility in water of about 34 mm (10). COS is stable when dissolved in acidified water but is hydrolyzed in alkaline solution to CO2 and H2S (10,25,29). Hydrolysis proceeds via the monothiocarbonate ion which is unstable at low ionic strength at room temperature (25,29).…”

Section: Relevant Physical and Chemical Properties Of Cosmentioning

confidence: 99%

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Use of Carbon Oxysulfide, a Structural Analog of CO₂, to Study Active CO₂ Transport in the Cyanobacterium Synechococcus UTEX 625

Miller¹,

Espie²,

Canvin³

1989

Plant Physiol.

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Carbon oxysulfide (carbonyl sulfide, COS) is a close structural analog of CO2. Although hydrolysis of COS (to CO2 and H2S) does occur at alkaline pH (>9), at pH 8.0 the rate of hydrolysis is slow enough to allow investigation of COS as a possible substrate and inhibitor of the active CO2 transport system of Synechococcus UTEX 625. A light-dependent uptake of COS was observed that was inhibited by CO2 and the ATPase inhibitor diethylstilbestrol.The COS taken up by the cells could not be recovered when the lights were tumed off or when acid was added. It was concluded that most of the COS taken up was hydrolyzed by intracellular carbonic anhydrase. The production of H2S was observed and COS removal from the medium was inhibited by ethoxyzolamide. Bovine erythrocyte carbonic anhydrase catalysed the stoichiometric hydrolysis of COS to H2S. The active transport of CO2 was inhibited by COS in an apparently competitive manner. When Natdependent HCO3-transport was allowed in the presence of COS, the extracellular [CO2] rose considerably above the equilibrium level. This CO2 appearing in the medium was derived from the dehydration of transported HCO3-and was leaked from the cells. In the presence of COS the return to the cells of this leaked CO2 was inhibited. These results showed that the Nat-dependent HCO3-transport was not inhibited by COS, whereas active CO2 transport was inhibited. When COS was removed by gassing with N2, a normal pattem of CO2 uptake was observed. The silicone fluid centrifugation method showed that COS (100 micromolar) had little effect upon the initial rate of HC03-transport or CO2 fixation. The steady state rate of CO2 fixation was, however, inhibited about 50% in the presence of COS. This inhibition can be at least partially explained by the significant leakage of CO2 from the cells that occurred when CO2 uptake was inhibited by COS. Neither CS2 nor N20 acted like COS. It is concluded that COS is an effective and selective inhibitor of active CO2 transport.

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Solvolysis ofN,N-dimethylthiocarbamoyl chloride: effect of sulfur-for-oxygen substitution upon kinetics and product partitioning

Kevill¹,

Rudolph²,

D’Souza³

2000

J. Phys. Org. Chem.

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A study of the solvolyses of N,N-dimethylcarbamoyl chloride (1) was extended to the solvolyses of N,N-dimethylthiocarbamoyl chloride (2). The specific rates of solvolysis of 2 at 0.0°C are two to three orders of magnitude greater than those for 1. Analysis of the data using the extended Grunwald-Winstein equation leads to sensitivities l and m and an l/m ratio which are lower for 2 than those previously reported for 1. Product selectivities in mixtures of water with ethanol or methanol indicate a greater preference for reaction with alcohol for 2. All observations can be rationalized in terms of the formation of a more stable carbocation from 2, leading to an earlier transition state, reduced nucleophilic solvation and the possibility of extensive progression to a free carbocation prior to product formation.

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238. The kinetics of the reaction between carbonyl sulphide and water

Cited by 33 publications

References 0 publications

The oceanic cycle and global atmospheric budget of carbonyl sulfide

The oceanic cycle and global atmospheric budget of carbonyl sulfide

Use of Carbon Oxysulfide, a Structural Analog of CO₂, to Study Active CO₂ Transport in the Cyanobacterium Synechococcus UTEX 625

Solvolysis ofN,N-dimethylthiocarbamoyl chloride: effect of sulfur-for-oxygen substitution upon kinetics and product partitioning

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238. The kinetics of the reaction between carbonyl sulphide and water

Cited by 33 publications

References 0 publications

The oceanic cycle and global atmospheric budget of carbonyl sulfide

The oceanic cycle and global atmospheric budget of carbonyl sulfide

Use of Carbon Oxysulfide, a Structural Analog of CO2, to Study Active CO2 Transport in the Cyanobacterium Synechococcus UTEX 625

Solvolysis ofN,N-dimethylthiocarbamoyl chloride: effect of sulfur-for-oxygen substitution upon kinetics and product partitioning

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Use of Carbon Oxysulfide, a Structural Analog of CO₂, to Study Active CO₂ Transport in the Cyanobacterium Synechococcus UTEX 625