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Electron and Proton Transfer by the Grotthuss Mechanism in Aqueous Solution and in Biological Systems; Transfert d'Electrons et de Protons par le Mecanisme de Grotthuss en Solution Aqueuse et dans les Systemes Biologiques; Perenos ehlektronov i protonov mekhanizmom grotkhusa v vodnom rastvore i v biologicheskikh sistemakh; Transferencia Electronica y Protonica por el Mecanismo de Grotthuss en Soluciones Acuosas y en Sistemas Biologicos

Conference:

Abstract

TheFe{sup ll}-Fe{sup III} electron-exchange reaction and certain long-range biological redox reactions involve the transfer of electrons by a Grotthuss-type mechanism over water bridges. The Grotthuss mechanism is also responsible for the anomalously great electrical conductivity of acidic aqueous solutions. At ordinary pressures the rate-determining step of the Grotthuss mechanism is the rotation of H{sub 2}O, or possibly H{sub 3}O+, and not the actual proton flip itself. The Grotthuss mechanism is confined to the ''free'' rotatable monomeric water between the Frank-Wen clusters in liquid water and avoids areas of relative order. The concentration dependence of protonic conduction can be represented by an equation based upon a cube root of concentration extrapolation and containing Arrhenius terms in which the activation energies are those for the rotation of and the formation of ''holes'' in the solvent water. Thus chemical energy and/or electrical energy can be transmitted rapidly over relatively great distances by the Grotthuss mechanism. Such processes are involved in a variety of phenomena of biological significance, examples being muscular contraction and the chemistry of the respiratory pigments. (author) [French] L'echange d'electrons dans Fe{sup II}-Fe{sup III} et certaines reactions biologiques d'oxydo-reduction a long terme font intervenir le transfert d'electrons par un mecanisme du  More>>
Authors:
Horne, R. A.; Courant, R. A.; Johnson, D. S. [1] 
  1. Arthur D. Little, Inc. Cambridge, MA (United States)
Publication Date:
Oct 15, 1965
Product Type:
Conference
Report Number:
IAEA-SM-64/19
Resource Relation:
Conference: Symposium on Exchange Reactions, Upton, NY (United States), 31 May - 4 Jun 1965; Other Information: 27 refs., 5 figs., 2 tabs.; Related Information: In: Exchange Reactions. Proceedings of the Symposium on Exchange Reactions| 430 p.
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACTIVATION ENERGY; AQUEOUS SOLUTIONS; CONCENTRATION RATIO; ELECTRIC CONDUCTIVITY; ELECTRON EXCHANGE; ELECTRON TRANSFER; EXTRAPOLATION; REDOX REACTIONS
OSTI ID:
22117353
Research Organizations:
International Atomic Energy Agency, Vienna (Austria)
Country of Origin:
IAEA
Language:
English
Other Identifying Numbers:
Other: ISSN 0074-1884; TRN: XA13M2437073974
Submitting Site:
INIS
Size:
page(s) 43-54
Announcement Date:
Aug 01, 2013

Conference:

Citation Formats

Horne, R. A., Courant, R. A., and Johnson, D. S. Electron and Proton Transfer by the Grotthuss Mechanism in Aqueous Solution and in Biological Systems; Transfert d'Electrons et de Protons par le Mecanisme de Grotthuss en Solution Aqueuse et dans les Systemes Biologiques; Perenos ehlektronov i protonov mekhanizmom grotkhusa v vodnom rastvore i v biologicheskikh sistemakh; Transferencia Electronica y Protonica por el Mecanismo de Grotthuss en Soluciones Acuosas y en Sistemas Biologicos. IAEA: N. p., 1965. Web.
Horne, R. A., Courant, R. A., & Johnson, D. S. Electron and Proton Transfer by the Grotthuss Mechanism in Aqueous Solution and in Biological Systems; Transfert d'Electrons et de Protons par le Mecanisme de Grotthuss en Solution Aqueuse et dans les Systemes Biologiques; Perenos ehlektronov i protonov mekhanizmom grotkhusa v vodnom rastvore i v biologicheskikh sistemakh; Transferencia Electronica y Protonica por el Mecanismo de Grotthuss en Soluciones Acuosas y en Sistemas Biologicos. IAEA.
Horne, R. A., Courant, R. A., and Johnson, D. S. 1965. "Electron and Proton Transfer by the Grotthuss Mechanism in Aqueous Solution and in Biological Systems; Transfert d'Electrons et de Protons par le Mecanisme de Grotthuss en Solution Aqueuse et dans les Systemes Biologiques; Perenos ehlektronov i protonov mekhanizmom grotkhusa v vodnom rastvore i v biologicheskikh sistemakh; Transferencia Electronica y Protonica por el Mecanismo de Grotthuss en Soluciones Acuosas y en Sistemas Biologicos." IAEA.
@misc{etde_22117353,
title = {Electron and Proton Transfer by the Grotthuss Mechanism in Aqueous Solution and in Biological Systems; Transfert d'Electrons et de Protons par le Mecanisme de Grotthuss en Solution Aqueuse et dans les Systemes Biologiques; Perenos ehlektronov i protonov mekhanizmom grotkhusa v vodnom rastvore i v biologicheskikh sistemakh; Transferencia Electronica y Protonica por el Mecanismo de Grotthuss en Soluciones Acuosas y en Sistemas Biologicos}
author = {Horne, R. A., Courant, R. A., and Johnson, D. S.}
abstractNote = {TheFe{sup ll}-Fe{sup III} electron-exchange reaction and certain long-range biological redox reactions involve the transfer of electrons by a Grotthuss-type mechanism over water bridges. The Grotthuss mechanism is also responsible for the anomalously great electrical conductivity of acidic aqueous solutions. At ordinary pressures the rate-determining step of the Grotthuss mechanism is the rotation of H{sub 2}O, or possibly H{sub 3}O+, and not the actual proton flip itself. The Grotthuss mechanism is confined to the ''free'' rotatable monomeric water between the Frank-Wen clusters in liquid water and avoids areas of relative order. The concentration dependence of protonic conduction can be represented by an equation based upon a cube root of concentration extrapolation and containing Arrhenius terms in which the activation energies are those for the rotation of and the formation of ''holes'' in the solvent water. Thus chemical energy and/or electrical energy can be transmitted rapidly over relatively great distances by the Grotthuss mechanism. Such processes are involved in a variety of phenomena of biological significance, examples being muscular contraction and the chemistry of the respiratory pigments. (author) [French] L'echange d'electrons dans Fe{sup II}-Fe{sup III} et certaines reactions biologiques d'oxydo-reduction a long terme font intervenir le transfert d'electrons par un mecanisme du type de Grotthuss sur des ponts d'eau. Le mecanisme de Grotthuss explique egalement la conductivite anormalement grande des solutions aqueuses d'acides. Sous les pressions ordinaires, l'etape du mecanisme de Grotthuss qui determine la vitesse est la rotation de H{sub 2}O ou peut-etre de H{sub 3}O+, et non pas le changement d'orientation du proton meme. Le mecanisme de Grotthuss est limite a l'eau monomerique ' libre ' , susceptible de rotation, entre les amas de Frank-Wen dans l'eau liquide et il evite les zones d'ordre relatif. On peut representer les variations de la conduction protonique selon la concentration par une equation, fondee sur la racine cubique de la concentration extrapolee, qui contient des termes d'Arrhenius ou les energies d'activation sont celles qui ont trait a la rotation de l'eau du solvant et a la formation de ' trous 'dans cette eau. Ainsi, l'energie chimique et l'energie electrique peuvent etre transmises rapidement par le mecanisme de Grotthuss sur des distances relativement grandes. Ces processus interviennent dans divers phenomenes importants en biologie, notamment dans la contraction musculaire et la chimie des pigments respiratoires. (author) [Spanish] El intercambio electronico Fe{sup II} - Fe{sup III}, asi como ciertas reacciones de oxidorreduccion biologica lenta, implican una transferencia de electrones en virtud de un mecanismo de Grotthuss pasando por puentes agua. A este mecanismo se debe asimismo la conductividad electrica, anormalmente elevada, de las soluciones acuosas de acidos. A presion ordinaria, la etapa que determina la velocidad del mecanismo de Grotthuss es la rotacion de la molecula de H{sub 2}O, posiblemente H{sub 3}O+, y no el propio salto del proton. El mecanismo de Grotthuss se limita al agua monomerica capaz de girar 'libremente' entre los grupos de Frank-Wen en agua liquida y no se verifica en las zonas relativamente ordenadas. La relacion entre la conduccion protonica y la concentracion se puede expresar mediante una ecuacion basada en la rafz ciibica de la concentracion extrapolada y que contiene terminos de Arrhenius en los cuales las energias de activacion son las correspondientes a la rotacion y a la formacion de 'huecos' en el agua disolvente. De este modo, la energia, sea quimica o electrica, puede ser transmitida rapidamente a distancias relativamente grandes por el mecanismo de Grotthuss. Estos procesos intervienen en numerosos fenomenos de importancia biologica, entre otros, la contraccion muscular y la quimica de los pigmentos respiratorios. (author) [Russian] Reakcija jelektronnogo Fe{sup II} - Fe{sup III} i nekotorye dolgovremennye biologicheskie reakcii okislenija-vosstanovlenija svjazany s perenosom jelek- tronov mehanizmom tipa Grothusa cherez vodjanye mostiki. Mehanizm Grothusa javljaetsja takzhe prichinoj anomal'no bol'shoj jelektroprovodnosti kislotnyh vodnyh rastvorov. Pri obychnyh davlenijah stupen'ju, opredeljajushhej skorost' mehanizma Grothusa, javljaetsja vrashhe- nie N{sub 2}O ili, vozmozhno N{sub 3}O+ , a ne dejstvitel'naja orientacija protonov. Mehanizm Grothusa ogranichivaetsja 'svobodnoj' vrashhajushhejsja monometricheskoj vodoj mezhdu skoplenijami Frank- Vena v zhidkoj vode i izbegaet oblastej otnositel'nogo porjadka. Zavisimost' protonnoj provodimosti ot koncentracii mozhet byt' predstavlena uravneniem, osnovannym na kubicheskom korne jekstrapoljacii koncentracii i soderzhashhim uslovija Arheniusa, pri kotoryh jenergii aktivacii javljajutsja jenergijami dlja vrashhenija i obrazovanija 'otverstij' v rastvorjajushhej vode. Takim obrazom, himicheskuju i jelektricheskuju jenergiju mozhno bystro peredavat' na sravnitel'no bol'shie rasstojanija s pomoshh'ju mehanizma Grothusa. Takie processy svjazany s rjadom javlenij, predstavljajushhih interes dlja biologii, primerami kotoryh javljajutsja myshechnoe sokrashhenie i himija dyhatel'nyh pigmentov. (author)}
place = {IAEA}
year = {1965}
month = {Oct}
}