Near hydration of ions in infinitely dilute solutions of hydrogen halogens: influence of temperature and pressure

doi:10.26565/2220-637X-2013-22-19

V. I. Bulavin V.N. Karazin Kharkiv National University
Ivan N. Vyunik V.N. Karazin Kharkiv National University
A. E. Savisko V.N. Karazin Kharkiv National University

DOI: https://doi.org/10.26565/2220-637X-2013-22-19

Keywords: water, proton, hydrogen halogens, negative hydratation, attraction coefficient, pressure, temperature, resolvation of proton, mechanism of proton transfer

Abstract

The calculation of attraction coefficient (ξ_а_t) in water for proton, chloride- and bromide-ion was carried out over the temperature range from 273.15 to 473.15 K and pressure range from 1 to 8000 kg/cm² using the literary limiting electrical conductance of these ions. Negative hydration of proton was identified at all temperatures and pressures on the basis of the results we obtained. The transformation from negative to positive hydration was revealed for chloride- and bromide-ion. Temperature and pressure range, when this transition is observable, were determined. It is shown, that negative solvation is connected with prevailing influence of short-range intermolecular interactions as compared to ion-molecular. The scheme of the supposed mechanism of prototropic transfer of proton is offered. This scheme includes transfer of hydronium and structural diffusion of Zundel cation in volume of “free solvent”.

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References

Bulavin V.I., Vyunnik I.N. Blizhnyaya solvatatsiya i podvizhnost’ ionov v predel’no razbav-lennykh spirtovykh i vodnykh rastvorakh galogenovodorodov //Ukr. Khimich. Zh.– 2012. – Т. 78. – № 8. – S. 82 – 91.

Klasternaya struktura vody (оbzor) / S.D. Zakharov, I.V. Моsyagina. – Моskva: FIAN. – 2011. – 24 s. (Preprint).

Pura S. Ion association anhydrous ferric chloride in primary alcohols at different temperatures //J. Mol. Liquids. – 2007. – V. 136. – № 1-2. – P. 64 – 70.

Agmon N. The Grotthuss mechanism //Chem. Phys. Lett. – 2005. – V. 244. – № 5-6. – P. 456 – 462.

Asthagiri D., Pratt L.R., Kress J.D. Ab initio molecular dynamic and quasichemical study of H+(aq)//Proc. Natl. Acad. Sci. USA.– 2005. – V. 244. – № 19. –P. 6704 –6708.

Markovitch O., Agmon N. Structure and energetics of the hydronium hydration shells // J. Phys. Chem. A. – 2007. – V. 111. –№ 12. –Р. 2253–2256.

Cukierman S. Proton mobilities in water and in different stereoisomers of covalently linked gramicidin A channels //Biophys. J. – 2000. –V. 78. – № 4. – P.1825–1834.

Markovitch O., Chen H., Izvekov S., Paesani F.,Voth G.A., Agmon N Special pair dance and partner selection: elementary steps in proton transport in liquid water //J. Phys. Chem. B.– 2008. – V. 112. –№ 31. – Р. 9456–9466.

Lagodzinskaya G.V., Yunda N.G., Маnelis G.B. Srukturnaya samoorganizatsiya v rastvorakh i na granitse razdela faz/ Оtv. red. А.Yu. Tsivaddze. – М.:zd-vo LKI. – 2008. – S. 200 – 261.

Kornyshev A.A., Kuznetsov A.M., Spohr E., Ulstrup J. Kinetics of proton transport in water //J. Phys. Chem. B.– 2003. – V. 107. – № 15. – Р. 3351–3366.

Kreuer K.-D., Paddison J.S., Spohr E., Schuster M. Transport in proton conductance for fuel-cell applications: simulations, elementary reactions, and phenomenology// Chem. Rev. – 2004. – V. 104. – № 10. – P. 4637 – 4678.

Voth G.A.Computer simulation of proton solvation and transport in aqueous and biomolecular systems // Acc. Chem. Res. – 2006.– V. 39. – № 2. – P. 143-150.

Sarkisov G.N. Strukturnye моdeli vody //Uspekhi fiz. nauk. – 2006. – Т. 146. – № 8. – S. 833 – 845.

Yao S.H., Lee J., Robinson G.W. Water structure affected by a week base //J. Am. Chem. Soc. – 1990. – V. 112. – № 15. – P. 5698 – 5700.

Urquidi J., Singh S., Cho C.H., Robinson G.W. Origin of temperature and pressure effects on radial distribution function of water//Phys. Rev. Lett. – 1999. – V. 103. – № 12. – P. 2348 – 2350.

Bulavin V.I., Vyunnik I.N. Vliyanie temperatury na anomal’nuyu elektricheskuyu provodi-most’ protona v beskonechno razbavlennykh spirtovykh rastvorakh iodovodoroda // Ukr. Khimich. Zh.– 2011. – Т. 77. – № 4. – S. 14 – 21.

Larionov E.G. Predel’naya ekvivalentnaya elektroprovodnost’ НСl i anomal’naya pod-vizhnost’ protona v vode pri temperaturakh do 150°С i davleniyakh dо 8000 kg/sм2 // Izv. SО АN SSSR. Ser. khim. – 1976. – №5 – S. 3-9.

Leopold K.R. Hydrated acid clusters//Ann. Rev. Phys. Chem. – 2011. – V. 62. – P. 327 –349.

Sамоjlov О.Ya. Struktura vodnykh rastvorov elektrolitov i gidratatsiya ionov.– М.: izd-vо АN SSSR. – 1957. – 183 s.

Vyunnik I.N., Каlugin О.N., Оtlejkina Е.P. Novyj parametr strukturnykh effektov ionov v rastvoritele // Vestn. Khark. un-ta. – 1998. –№2, khimiya. – S. 149-152.

Yukhnevich G.V., Таrаkаnovа Е.G., Маjоrov V.D., Librovich N.B. Struktura sol’vatov pro-tona v rastvorakh i ikh kolebatel’nye spektry // Uspekhi khimii. –1995. – Т. 64, № 10. – S. 963-974.

Erdei-Gruz Т. Yavleniya perenosa v vodnykh rastvorakh. – М.: Мir. – 1976. – 596 s.

Larionov E.G. К raschеtu predel’noj elektroprovodnosti individual’nych ionov pri vysokikh temperaturach i davleniyakh // Izv. SО АN SSSR. Ser. khiм. – 1976. – №6 – S. 3-9.

Кratkij spravochnik fiziko-khimicheskikh velichin / А.А. Ravdel’, А.М. Ponomareva – Izd-vо Spez. Lit., 1983. – 232 s.

Vdovenko V.М., Gurikov Yu.V., Legnin Е.К. Теrмоdinamika dvukhstrukturnoj modeli vody. I. О structure tyazheloj vody //Zh. Struktutrn. khimii. – 1966. – Т. 7. – № 6. – S. 819 – 824.

Sамоjlov О.Ya., Nosova Т.А. Strukturnye оsobennosti vody// Zh. Struktutrn. khimii. – 1965. – Т. 6. – № 5. – S. 798 – 808.

Krynicki K., Green C.D., Sawyer D.W. Pressure and temperature dependence of self-diffusion in water//Faraday Discuss. Chem. Soc. – 1978. – V. 66. – P. 199-208.

Bulavin V.I., Vyunnik I.N. Mezhionnye vzaimodejstviya v spirtovykh rastvorakh elektrolitov //Zh. fizich. khim. – 2008. – Т. 82. – № 9. – S. 1681 – 1684.

Zhuravlev V.I., Usacheva Т.М. Ravnovesnye dielektricheskie svojstva butandiolov// Vestn. Моsk. un-ta. Ser. 2. Khimiya. – 2010. –Т.51. – № 4. – S. 274 –278.

Horne N.A., Axelrod E.H Proton mobility and electron exchange in aqueous media // J.Chem. Phys. – 1964. – Vol. 40, №6. – Р. 1518-1522.

Gorbatyj Yu.Е. Vozmozhnosti difraktsionnykh metodov v issledovanii vodnykh sistem pri vy-sokikh temperaturakh i davleniyakh// Теrmodinamicheskie svojstva rastvorov pri ekstre-mal’nykh usloviyakh. Меzhvuz. sborn. nauchn. trudov. – Ivanovo. – 1986. – S. 83-91.

Frank H.S., Wen W.V. Ion-solvent interaction in aqueous solutions: a suggested picture of water structure // Disc. Faraday Soc. – 1957. – Vol. 24. – P. 133-140.

Korol’kov D.V., Skorobogatov G.А. Теоreticheskaya khimiya. Uchebnik. – 2005. – St.Petersburg: izd-vо St.Petersburgsk. un-ta. – 656 s.