The Formation of Water and Hydrogen Peroxide at Low Pressures

Rodebush, W. H.; Wende, Christina; Campbell, R. W.

doi:10.1021/ja01289a040

Cited by 11 publications

(12 citation statements)

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“…Earlier work (16,14) has shown that both water and l~ydrogen peroxide are obtained a t liquid air temperatures but only water is obtained a t -78°C. In the present study, product yields were determined as a function of trapping temperature over the intervening range.…”

Section: Influence Of Trapping Temperaturementioning

confidence: 98%

“…Several mecha~lisms have been proposed (2,16,19) to explain the formation of these final products from the hydrogen atoms and hydroxyl radicals formed initially in the disAKanzcscript…”

Section: Introductionmentioning

confidence: 99%

“…Recently, the assumpti011 has again been made that the water vapor discharge call serve as a source of hydroxyl radicals (9). 'Several investigations have shown that the final products of the decomposition are hydrogen, oxygen, water, and hydrogen peroxide in proportions which depend upon experimental conditions, including temperature (4), pressure (16), surface (16), and the presence of catalysts (17). Several mecha~lisms have been proposed (2,16,19) to explain the formation of these final products from the hydrogen atoms and hydroxyl radicals formed initially in the dis-charge, but some of the suggestions were based on an incomplete knowledge of the over-all reaction.…”

Section: Introductionmentioning

confidence: 99%

“…'Several investigations have shown that the final products of the decomposition are hydrogen, oxygen, water, and hydrogen peroxide in proportions which depend upon experimental conditions, including temperature (4), pressure (16), surface (16), and the presence of catalysts (17). Several mecha~lisms have been proposed (2,16,19) to explain the formation of these final products from the hydrogen atoms and hydroxyl radicals formed initially in the dis-charge, but some of the suggestions were based on an incomplete knowledge of the over-all reaction. Rodebush has recently proposed a mechanism which postulated the existence in the active gases of a high concentration of hydroxyl radicals which disappear in the gas phase a t ordinary temperatures by an overall reaction OH + OH 4 He+ 0 2 , while a t very low temperatures they condense to hydrogen peroxide (14).…”

Section: Introductionmentioning

confidence: 99%

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Reactions in Dissociated Water Vapor

Jones¹,

Winkler²

1951

Can. J. Chem.

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Water vapor dissociated by an electric discharge and passed into a cold trap yielded products which gave off oxygen a t temperatures above -120°C. and a t room temperature consisted of hydrogen peroxide and water. With products formed under given conditions, the amount of oxygen evolved with warming was proportional to the total amount of product and independent of the warming procedure. The evolution proceeded t o completion a t -7g°C. Water was found a t all trap temperatures between -78°C. and -195°C.Hydrogen peroxide was formed only if the trap temperature was below -120°C.. and oxygen was evolved only from products formed below -150°C.The yields of water, hydrogen peroxide, and evolved oxygen all increased with decreasing trap temperature. As the volume of reaction chambers inserted between the discharge tube and the trap was increased, the yield of hydrogen pergxide decreased continuously, while the yield of water a t first decreased and then increased to a limiting value. Packing a given reaction chamber with glass wool drastically reduced the yield of hydrogen peroxide, b u t had littleeffect on the yield of water. PacGing the trap itself had only a slight effect on the yields. The results are co~npared with those obtained by others with the H-On system a t low temperatures, and a mechanism is proposed to correlate the two systems. IntroductionWhen water vapor a t low pressures is subjected to the action of a glow discharge of moderate current strength, the primary decomposition products are hydrogen atoms and free hydroxyl radicals (11). If the water vapor is passed continuously through the discharge, the effluent gases have characteristic properties, not all of which can be due to atonlic hydrogen alone (3, 7, 18). The possible presence of hydroxyl radicals in these gases has been a matter of controversy. Early workers (18,7,8) assumed their presence on the basis of apparently faulty spectroscopic evidence. Subsequently Bonhoeffer and Pearson (2) deduced from spectroscopic data that the hydroxyl radicals disappear so rapidly that no appreciable number could survive outside the discharge. This was contradicted by the results of Oldenberg and his coworkers, who showed with a more refined technique that the hydroxyl absorption spectrum persisted in the discharge tube for a t least 0.4 second after the current was interrupted (10,11,12). Recently, the assumpti011 has again been made that the water vapor discharge call serve as a source of hydroxyl radicals (9).'Several investigations have shown that the final products of the decomposition are hydrogen, oxygen, water, and hydrogen peroxide in proportions which depend upon experimental conditions, including temperature (4), pressure (16), surface (16), and the presence of catalysts (17). Several mecha~lisms have been proposed (2,16,19) to explain the formation of these final products from the hydrogen atoms and hydroxyl radicals formed initially in the disAKanzcscript

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Section: Influence Of Trapping Temperaturementioning

confidence: 98%

“…Several mecha~lisms have been proposed (2,16,19) to explain the formation of these final products from the hydrogen atoms and hydroxyl radicals formed initially in the disAKanzcscript…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Reactions in Dissociated Water Vapor

Jones¹,

Winkler²

1951

Can. J. Chem.

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“…However, the early experiments of Geib and Harteck (31,32), and Rodebush and coworkers (33,34), show that when oxygen is added to a stream of hydrogen atoms or water vapor is dissociated in the discharge, other complex surface reactions occur which produce mainly H, and 0, at room temperature and H,O, at liquid N, temperatures. Foner and Hudson (35) have reported OH radicals coming from the surfacein the H-0, system at room temperature.…”

Section: Surface Reactionsmentioning

confidence: 99%

Homogeneous rate of recombination of hydrogen atoms

Larkin¹

1968

Can. J. Chem.

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The rate of decay of hydrogen atoms has been measured in a conventional type of discharge-flow system at temperatures between 190-350 OK. The recombination fitted the equation where Ic, is the first order surface rate constant. No three-body recombination for M = H was observed at the low levels of dissociation (2-5 %) employed. When the flow gases contained traces of water vapor and (or) oxygen as impurities, the homogeneous rate constants (k,,,) had a small positive activation energy which was due to the influence of a surface reaction between hydrogen atoms and the impurities.In the absence of impurities, true homogeneous rate constants were obtained. A value of k,,,, = 4.6 + 0.5 x 1015 cm6 mole-' s-' was found at 291 OK. The temperature variation was approximately T-'1' over the range 19G350 OK.

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Photochemie Im Schumann‐ultraviolett

Groth

1939

Zeitschrift für Elektrochemie und angewandte physikalische Chem

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The Formation of Water and Hydrogen Peroxide at Low Pressures

Cited by 11 publications

References 0 publications

Reactions in Dissociated Water Vapor

Reactions in Dissociated Water Vapor

Homogeneous rate of recombination of hydrogen atoms

Photochemie Im Schumann‐ultraviolett

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